Cure-indicating molding and coating composition

ABSTRACT

The present invention provides novel hydrosilation-curable compositions, the cure of which can be monitored visually, comprising: (1) an ethylenic compound; (2) a compound containing silicon-bonded-hydrogen groups; (3) a hydrosilation catalyst; and (4) one or more cure-indicating dyes with light absorption in the visible spectrum that exhibit a color change in the presence of a silicon-bonded-hydrogen compound and a precious metal hydrosilation catalyst. The cure-indicating dye provides the composition with an initial pre-cure color and a different post-cure color. As a result of this change in color, the state of cure of the composition can be visually monitored.

This application is a continuation in part of application Ser. No.268,335 filed Jun. 30, 1994, now abandoned.

FIELD OF THE INVENTION

This invention relates to cure-indicating compositions, whichcompositions are useful for preparing sealants, caulks, adhesives,potting materials, coatings (e.g., release liners) and moldingmaterials. This invention further relates to cure-indicatingpolysiloxane compositions, which compositions are useful for preparingdental impressions, otologic impressions, and medical and dentalimplants. This invention also relates to compositions and methods forvisually indicating a cure point of a hydrosilation-curabic composition(e.g., a silicone composition) via a color change.

RELATED APPLICATIONS

Of related interest is the following U.S. Patent Application, filed oneven date herewith by the assignee of this invention: "Dental ImpressionMaterial with Cure-indicating Dye," U.S. Ser. No. 496,772 filed Jun. 29,1995, which is herein incorporated by reference.

BACKGROUND OF THE INVENTION

Many materials undergo a change in state as a result of a "curingreaction." For example, as a result of a curing reaction a liquid resincomposition can be changed into a solid or elastomeric material. Thecuring reaction can be initiated in a number of different ways,including for example, heating the uncured sample, mixing two or morereactive components together, or exposing the uncured material to anactivating radiation source or electron beam energy. Depending on themethod of curing employed the transition time between states can vary inlength. For some materials the change in state may be observed by simplyprobing the material and observing a change in viscosity. Thistechnique, however, is subject to error and misinterpretation in manycases. In addition, manually probing samples may damage the sample, andmay not indicate small but important changes in the extent of cure.Other techniques of observing a material's change in state includemonitoring the rheological properties of the material, or analyticallymonitoring the material (e.g., using an instrument such as an NMR probeto observe directly a change in the functional groups of the material).Unfortunately, these direct techniques are often not practical for theroutine monitoring of a cure reaction or may be invasive or destructiveof the sample being monitored.

One example of a material that undergoes a curing reaction is a siliconematerial. "Silicones" are synthetic polymeric materials that possess anextraordinarily wide range of physical properties. They can be low- orhigh-viscosity liquids, solid resins, or vulcanizable gums. They displayan unusual combination of organic and inorganic chemical properties thatare due to their unique molecular structure of alternating silicon andoxygen atoms. One typical polysiloxane polymer is depicted below informula F1. ##STR1## These silicone polymers may be made by anequilibrium process from other siloxanes and typically range inviscosity from about 0.01 Pa s to 2500 Pa s. Silicone polymers can bemixed with other chemicals and fillers into an enormous variety ofproducts that serve in a multitude of applications.

Vulcanizing silicones are a special class of silicones that have as acommon attribute the development of a "crosslinked" elastomer fromrelatively low molecular weight polymers by means of a chemical reactionthat forms these crosslinks and effectively extends chain lengthsimultaneously. Vulcanizing silicones (e.g., addition-cure silicones)have many applications in industry including use as sealants, caulks,adhesives, coatings, potting materials, release liners, otologicimpression materials, molding materials, dental impression materials andmedical and dental implants. An essential ingredient in a vulcanizingsilicone is a crosslinking component (hereinafter the "crosslinker")that reacts with the "functional group" or groups (e.g., R¹ and R² offigure F1) of the polymer chains to simultaneously lengthen them andconnect them laterally to form the crosslinked network characteristic ofa silicone elastomer. Usually a catalytic agent is included tofacilitate the reaction of the crosslinker with the polymer's functionalgroups.

There are many types of vulcanizing silicones and likewise many types ofcrosslinking components and catalysts. Two such systems include (i)condensation-cured silicones and (ii) addition-cured, e.g.,hydrosilylation cured (alternatively spelled "hydrosilation") silicones.Condensation-cured silicones characteristically, and in many instancesdetrimentally, release water (or alcohol) as a by-product of thecrosslinking reaction. The crosslinking reaction in these systems istriggered typically by combining the silicone polymer, the crosslinkerand the catalyst. A variety of catalysts initiate and acceleratecondensation curing such as amines and carboxylic acid salts of tin. Atlow temperatures the condensation-cured silicone typically requires longtimes to fully cure (hours or even days). Higher catalyst concentrationsand/or higher temperatures can shorten the cure time.

Addition-cured silicones (e.g., hydrosilylation cured silicones) aregenerally considered to be of higher quality and are dimensionally moreaccurate than condensation-cured silicones. Unlike condensation-curedsilicones, addition-cured silicones, e.g., hydrosilation-curedsilicones, do not produce detrimental by-products during curing. Suchsilicones differ from condensation-cured silicones in that thehydrosilation-cured composition typically contains:

(1) a polymer which contains two or more vinyl functional groups;

(2) a "hydrosilane" crosslinker component containing two or more SiHbonds; and

(3) a precious metal catalyst such as a platinum catalyst.

A particularly preferred addition-cured silicone is formed by reacting(1) a multiply-vinyl-containing organopolysiloxane with (2) anorganopolysiloxane containing a multiplicity of SiH bond per molecule(hereinafter "organohydropolysiloxane"). This reaction is typicallyfacilitated by the presence of (3) a platinum catalyst of the Karstedttype. Platinum catalysts of the Karstedt type are described in U.S. Pat.Nos. 3,715,334, 3,775,452 and 3,814,730 which are herein incorporated byreference.

When vulcanizing silicones are used as modeling compounds (e.g., dentalimpression materials) it is customary to provide the compound to theuser as two separate mixtures (i.e., the hydrosilation catalyst isstored separately from the hydrosilane crosslinker). When the user isready to prepare an impression or model, the two parts will be mixedtogether, the silicone will be placed against the surface or object tobe modeled and then the user will wait until the silicone completelycures. The cured silicone is then removed from the surface or object andretains a negative impression of that surface. A positive model may thenbe formed by filling the impression cavity with a material such as waxor plaster of Paris. In many instances it may not be feasible to formthe positive model immediately. Therefore, it is also important that theimpression retains its dimensional accuracy over a long period of time(often weeks or months).

The setting reaction of a vulcanizing silicone is triggered, in general,by the mixing together of the catalyst, crosslinker and polymer. Byvarying the amount of catalyst and crosslinker, the rate of setting maybe adjusted. The rate of setting may be further adjusted by theincorporation of well known inhibitors and/or retarders. One suchinhibitor is 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane.These retarders often operate by reacting competitively with thecatalyst thereby slowing the crosslinking reaction. In general, with theslowing of the reaction both the working time and the setting time (asdefined below) are affected.

As the material begins to set, its viscosity increases. Eventually, themixture becomes "gelled" and is changed irreversibly into a crosslinkedpolymer or an "elastomer." At the gel-point the material no longereasily flows or adapts to new shapes. Therefore, in applications such asthe taking of a dental impression this period of time defines the extentof the "working time" period.

When the reaction is complete (or "practically" complete) the materialis said to be "set." This "setting time" is likewise an importantparameter for a silicone impression material, as it is crucial that thematerial remain in contact with the surface it is to replicate until ithas completely set. For dental impressions it is desirable to have arelatively short setting time (e.g., less than 10 minutes). Prematureremoval from the surface being replicated may result in a distortedimpression which will continue to crosslink, in the distorted position,outside of the mouth. Unfortunately, this situation is often unnoticedby the dentist initially and is discovered only after an expensive, butworthless, dental appliance has been fabricated. The dentist and patientmust then go through the entire lengthy impression making and appliancefabrication process again. This is a great expense and inconvenience.

For applications requiring detailed reproduction, such as dentalimpression materials, the setting time and the working time parametersare very important and must be carefully controlled. As previouslymentioned, the working time measures the time period over which thereacting silicone material remains fluid enough to flow and changeshape. After the reaction has reached the "gel point" the material'sproperties change drastically and resist further fluid flow. It isdesirable to have sufficient working time so that the dentist mayeasily, and prior to gelation, (1) mix the materials and (2) place themin the mouth.

One major factor which affects both the working time and the settingtime (in addition to the aforementioned use of an inhibitor or retarder)is the catalyst's "activity." Unfortunately, platinum catalysts of theKarstedt variety are somewhat sensitive to degradation and therefore areof variable activity. While the exact mechanism is presently unknown,this degradation may be advanced at high temperatures (such as might beencountered in a hot warehouse or in a truck-trailer). Over time thecatalyst composition is believed to degrade and the setting time of themixed composition becomes longer and longer. As previously mentionedeven small changes in the setting time can have a detrimental effect onthe accuracy of an impression if the user removes the material prior toits complete cure. Such early removal becomes more likely if thecatalyst activity unexpectedly decreases upon storage. Another majorfactor which affects both the working time and the setting time is theratio of catalyst to crosslinker. This ratio may be adjusted (purposelyor inadvertently) by varying the amounts of each paste in the mix.

Various approaches have been attempted to provide an indication of amaterial's extent of cure. For example, U.S. Pat. Nos. 5,047,444;5,118,559; and 5,182,316 describe curable compositions that can bemonitored for extent of cure via detection of a UV fluorophore which isgenerated during the curing process. These compositions require the useof both a UV irradiation source and a UV fluorescence detector tomonitor the extent of cure effectively and cannot be visualized by thenaked eye. U.S. Pat. No. 3,509,081 describes the use, in a condensationsilicone composition, of a dye that exhibits a visible color change atthe desired degree of cure. This system is apparently limited andunpredictable, since, as the inventors state, it is "believed there isno technical relationship between the desired cure and the ultimatecolor change." In addition, as previously mentioned condensationsilicones are limited by their dimensional instability. European PatentApplication 0 492 830 A2 describes a method, for ultraviolet radiationcuring compositions, of indicating a cure point by color change.Compositions of this invention comprise free-radical-curable materials,UV activated free-radical initiators, and a dye that changes color uponexposure to ultraviolet radiation in the presence offree-radical-generating photoinitiators. Preferred dyes of thisinvention include anthraquinone and bis-azo dyes. U.S. Pat. No.4,788,240 discloses compositions comprising a polyorganosiloxane havingtwo or more alkenyl radicals, a polyorganohydrogensiloxane, a platinumor platinum compound catalyst, and an anthraquinone or azo dye. Thecompositions are described as being useful as a molding or dentalimpression material. Materials exemplified in this patent requireextended curing times which are undesirable for many dental procedures.

SUMMARY OF THE INVENTION

This invention relates to compositions and methods for indicatingvisually a cure point of a hydrosilation-curable composition (e.g., asilicone composition) via a color change.

The present invention provides novel hydrosilation-curable compositions,the cure of which can be monitored visually, comprising: (1) amultiply-ethylenic compound; (2) a compound containing a multiplicity ofsilicon-bonded-hydrogen groups; (3) a metal or metal complex capable ofcatalyzing a hydrosilation reaction; and (4) one or more cure-indicatingdye compounds with light absorption or emission in the visible spectrum(i.e., 400-800 nm) that exhibit a color change in the presence of asilicon-bonded-hydrogen compound and a precious metal hydrosilationcatalyst.

The present invention provides, in another aspect, compositions (e.g.,silicone compositions) which are useful for preparing sealants, caulks,adhesives, coatings, impression materials, molding materials,lithographic plates, release liners, potting materials and reflectivesheets. The silicone compositions of the present invention, the cure ofwhich can be monitored visually, comprise: (a) a curable siliconepolymer, e.g., vinyl-containing organopolysiloxane; (b) a crosslinker,e.g., an organopolysiloxane containing a multiplicity of SiH bonds; (c)a catalyst such as a platinum or precious metal containing hydrosilationcatalyst; and (d) one or more cure-indicating dyes that exhibit a colorchange in the presence of a silicon-bonded hydrogen compound and aprecious metal hydrosilation catalyst. Presently preferred optionalingredients of the silicone composition include fillers (e.g.,pulverized metals, silica, quartz, calcium carbonate or metal oxides),appropriate polymerization initiators and inhibitors, pigments,stabilizers, surfactants, modifying agents, indicator adjuvants, andcopolymerizable and non-copolymerizable cosolvents, and the like.Preferred dental impression "putties" of the present invention comprisebetween about 20 and 90 weight percent filler, more preferably betweenabout 40 and 80 weight percent filler, and most preferably between about60 and 80 weight percent filler. Preferred dental impression "washes"(or "single phase" syringeable materials) comprise between about 10 and70 weight percent filler, more preferably between about 20 and 60 weightpercent filler, and most preferably between about 30 and 60 weightpercent filler.

The curable silicone composition of the present invention can beprepared by combining (e.g., mixing together) the vinyl-containingorganopolysiloxane, the organohydropolysiloxane, the platinum catalystand the cure-indicating dye or dyes. In one embodiment, the componentsare pre-mixed into preferably two parts prior to use. For example, part"A" may contain the vinyl-containing organopolysiloxane, the platinumcatalyst and the cure-indicating dye, while part "B" may contain theorganohydropolysiloxane and optionally vinyl-containingorganopolysiloxane. Alternatively, the cure-indicating dye may beincorporated in part "B" and not in part "A", or may be in both parts"A" and "B". In another embodiment, the components are provided in onepart and further contain an ingredient (e.g., a catalyst inhibitor)which inhibits the cure reaction. Hydrosilation inhibitors are wellknown in the an and include such compounds as acetylenic alcohols,certain polyolefinic siloxanes, pyridine, acrylonitrile, organicphosphines and phosphites, unsaturated amides, and alkyl maleates. Forexample, an acetylenic alcohol compound can inhibit certain platinumcatalysts and prevent curing from occurring at low temperatures. Uponheating, the composition begins to cure. The amount of catalystinhibitor can vary up to about 10 times or more of the amount ofcatalyst, depending upon the activity of the catalyst and the shelf lifedesired for the composition. Alternatively, one may utilize a one-partcomposition comprising a cure-indicating dye, a vinyl-containingorganopolysiloxane, an organohydropolysiloxane, and a platinum catalystsuch as disclosed in U.S. Pat. Nos. 4,530,879, 4,510,094, 4,916,169,5,145,886 and patent application Ser. Nos. 07/626,904 and 07/627,009,both pending. Such one-part compositions are stable at room temperatureand cure when the catalyst is exposed to visible radiation.

A "cure-indicating dye" is added to the curable composition to provide avisual indication of the extent of the hydrosilation reaction (e.g.,extent of the crosslinking reaction). The cure-indicating dye exhibits acolor change in the presence of a silicon-bonded-hydrogen compound and aprecious metal hydrosilation catalyst and is characterized in a curablecomposition by having a first color before the cure reaction is effectedand a second color after the cure reaction has been effected to theindication point. The first color and second colors are sufficientlydifferent (or have a sufficiently different intensity) and may bereadily observed in the composition using the naked eye or, optionally,a suitable instrument such as a spectrophotometer, colorimeter orfluorimeter. The term "color" is here understood to include visiblefluorescence when examined using light of a shorter wavelength,including "black light".

The compositions of the present invention may find utility in a varietyof applications in which the visual identification of various stages ofcuring (such as working-time or setting-time) provides a benefit to theend-user. This feature is particularly beneficial in uses such as thetaking of a dental impression where the timing of the cure can affectthe quality of the impression. For example, if the dentist removes theimpression material from the mouth before it is fully set the impressionwill likely become distorted as it continues to cure. Similarly, if thedentist delays too long, e.g., after mixing the impression material,when placing the material against the teeth, the material will notreadily flow against the teeth and therefore not take an accurateimpression of them. Each or both of these situations can be avoided byutilizing visual cure indications of the present invention.

Alternatively, these compositions may be used to prepare adhesives,caulking materials, gaskets, sealants, coatings, potting materials orany other application where a cure-indicating material is required.Preferred applications of this invention include areas in whichnon-stick or low-energy properties of a surface are required such asimpression materials, modeling materials or in release coatings for usewith pressure-sensitive adhesives.

DEFINITIONS

The term "crosslinked polymer," as used herein, refers to polymers thatreact with the functional group or groups of the polymer chains (e.g.,R¹ and R² of figure F1) simultaneously to lengthen them and connect themlaterally, e.g., to form the crosslinked network characteristic of asilicone elastomer. In contrast to a thermoplastic polymer (i.e., apolymer that softens and flows upon heating) a crosslinked polymer,after crosslinking, is characteristically incapable of further flow.

The term "Silicone," as used herein, refers to a polymer having, for themost part, alternating silicon and oxygen atoms (i.e., a polysiloxanechemical structure) and having sufficient pendant functional groups toundergo a setting reaction in the presence of a crosslinker compound anda catalyst compound.

The term "vulcanizing," as used herein, refers to silicones that have asa common attribute the development of a crosslinked elastomer fromrelatively low molecular weight linear or branched polymers by means ofa chemical reaction that simultaneously forms these crosslinks andeffectively extends chain length at room temperature. "Room temperaturevulcanizing" ("RTV") implies that the curing reaction can proceed attemperatures at or near 25° C. For example, the oral cavity of the mouthhas an average temperature of approximately 32° C. and is therefore nearroom temperature. Certain "high" temperature cured materials aredesigned to cure only at relatively high temperatures (e.g., >50° C.or >100° C.) and are stable (i.e., the curing reaction is retarded) atroom temperature for prolonged periods.

The term "compound" is a chemical substance which has a particularmolecular identity or is made of a mixture of such substances, e.g.,polymeric substances.

The term "hydrosilation" means the addition of an organosilicon hydridecompound to a compound containing an aliphatic multiple bond (e.g., anolefinic or acetylenic unsaturation), preferably a vinyl group,--CH═CH₂.

The term "working time" as used herein, refers to the time between theinitiation of the setting reaction (e.g., when the vinyl-containingorganopolysiloxane, the organohydropolysiloxane, and the platinumcatalyst are mixed) and the time the setting reaction has proceeded tothe point at which it is no longer practical to perform further physicalwork upon the system, e.g., reform it, for its intended purpose. Whenthe reaction has proceeded to this later point the material is said tohave reached its "gel point." The working time preferably providesenough time to mix and place the composition into its desired form. Formany dental impression compositions and applications the working timeunder conditions of use is preferably greater than 30 seconds, morepreferably greater than 1 minute and most preferably greater than 2minutes.

The terms "set time" or "setting time" as used herein, refer to the timeat which sufficient curing has occurred so that essentially thematerial's final cured-state properties are obtained. For a siliconeimpression material the set time is that time at which one may removethe material from the surface being replicated without causing permanentdeformation of the silicone material. The setting time may beapproximated, for example, by measuring the torque of the reactingcomposition on a oscillatory rheometer. When the torque value reaches amaximum value the material is said to be fully set. An arbitrary torquevalue which is less than the typical maximum value (e.g. 90% of themaximum value) may alternatively be used as a practical approximation ofthe set time. In general, shorter setting times are preferred overlonger setting times. For dental impression compositions the settingtime occurs at a time preferably less than 10 minutes after initiationof the reaction. More preferably the setting time is less than the sumof 5 minutes plus the working time. Most preferably the setting time isjust longer than the desired working time.

As used herein, "solubility" means the capability of a substance to forma solution, i.e., either a true solution or a colloidal solution. A truesolution is a uniformly dispersed mixture at the molecular or ioniclevel of one or more substances (the solute) in one or more substances(the solvent). A colloidal dispersion is often called a solution. Sincecolloidal particles are larger than molecules it is strictly incorrectto call such dispersions solutions; however this term is widely used inthe literature, especially when the mixture is only slightly milky. Asused herein, "dispersibility" means the capability of a substance toform a dispersion, i.e., a two-phase system where one phase consists offinely divided particles (often in the colloidal size range) distributedthroughout a bulk substance, the particles being the disperse orinternal phase and the bulk substance the continuous or external phase.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides novel hydrosilation-curable compositions,the cure of which can be monitored visually, comprising: (1) amultiply-ethylenic compound; (2) a compound containing a multiplicity ofsilicon-bonded-hydrogen groups; (3) a metal or metal complex capable ofcatalyzing a hydrosilation reaction; and (4) one or more cure-indicatingdye compounds with light absorption or emission in the visible spectrum(i.e., 400-800 nm) that exhibit a color (including fluorescence) changein the presence of a silicon-bonded-hydrogen compound and a preciousmetal hydrosilation catalyst. The cure-indicating dye provides thecomposition with an initial pre-cure color (which color optionally canbe mixed with a colored non-cure-indicating dye or pigment) and adifferent post-cure color. As a result of this change in color, thesetting reaction or curing of the composition can be monitored visually.For example, this cure indication prompts the user to avoid exceedingthe working time of the composition or to avoid prematurely removing orstressing the composition prior to its being fully set.

In the practice of the present invention, the curable composition can bea multiple-part composition cured by combining crosslinking agents andcatalysts or a single-part composition cured by heating and/or exposureto actinic radiation or electron beam energy. Presently most preferredfor dental applications are two-pan addition-cure compositions of theroom temperature vulcanizing ("RTV") variety. The composition contains a"curable silicone polymer," that is, a polysiloxane having two or morefunctional groups, e.g., vinyl groups, which enable the polymer to bepolymerized or cured to a state of higher molecular weight. Suitablesilicone polymers are well-known in the an and are described, forexample, in "Silicones," Kirk-Othmer Encyclopedia of ChemicalTechnology, 3rd Ed., 20, 922-962 (1982).

Suitable ethylenic compounds for use in the present invention includethose compounds which undergo a crosslinking reaction with asilicon-bonded-hydrogen compound (alternatively referred to as the "SiHcompound" or "crosslinker") in the presence of a hydrosilation catalyst.Typically, the crosslinking reaction is facilitated by a catalystcompound and may be affected by temperature (e.g., the reaction mayproceed at a somewhat greater rate at an elevated temperature oralternatively may be initiated at an elevated temperature). Preferredethylenic compounds include monomers, oligomers or polymers whichcomprise pendant or terminal ethylenic "functional" groups (i.e., groupswhich "function" by reacting with the aforementioned SiH compound in thepresence of a catalyst) such as vinyl, alkenyl or cycloalkenyl groups.Alternatively, the functional group may be situated along the polymerchain (i.e., along the backbone) and not be in a pendant position. Ofthese, vinyl groups are more preferred, and terminal vinyl groups aremost preferred. It is understood that, in general, the curedcomposition's backbone "network" or "structure" comprises both theformerly ethylenic compound and the compound which contained the SiHgroup. It is understood that either compound could be employed ingreater or lesser proportion or have greater or lesser initial molecularweight. Furthermore, depending on the combination of ethylenic compoundand SiH compound, one could utilize a broad variety of "backbones" inthese compounds and thereby achieve a broad variety of curedcompositions having a range of physical properties.

Compounds containing aliphatic unsaturation which are useful in thepresent invention have olefinic or acetylenic unsaturation. Thesecompounds are well-known in the an of hydrosilation and are disclosed insuch patents as U.S. Pat. No. 3,159,662 (Ashby), U.S. Pat. No. 3,220,972(Lamoreaux), and U.S. Pat. No. 3,410,886 (Joy). In instances where theseunsaturated compounds contain elements other than carbon and hydrogen,it is preferred that these elements be either oxygen, nitrogen, silicon,halogen, or a combination thereof. The unsaturated aliphatic compoundmust contain two or more carbon-to-carbon multiple bonds. Representativeexamples of the aliphatically unsaturated hydrocarbons which can beemployed include diolefins, for example, divinylbenzene, and1,5-hexadiene. The unsaturated aliphatic compounds can have up to 20 to30 carbon atoms, or more.

Oxygen-containing unsaturated aliphatic compounds can also be used,especially where the unsaturation is ethylenic, such as divinylether,diallyl ether of ethylene glycol, diallyl ether, diallyl adipate,resorcinol, diallyl ether ω-undecenyl, ω-undecylenate (10-undecenoate),allyl acrylate, allyl methacrylate, and linolenic acid methyl ester.

Halogenated derivatives of the previously mentioned unsaturatedaliphatic compounds can be employed, including acyl chlorides as well ascompounds containing a halogen substituent on a carbon atom other than acarbonyl carbon atom. Unsaturated compounds containing nitrogensubstituents are also useful in the practice of the present invention.

Other unsaturated compounds useful in the practice of the presentinvention include polymers containing aliphatic unsaturation, such asthe polyester resins prepared from polybasic saturated or unsaturatedacids with polyhydric unsaturated alcohols, and the polyester resinsprepared by reacting unsaturated polybasic acids with saturatedpolyhydric alcohols.

As previously mentioned, one presently preferred class of compounds foruse in the present invention comprises a silicone backbone and two ormore functional groups. One typical silicone composition is thepolysiloxane referred to earlier and as depicted in formula F1. ##STR2##Usually these polymers are made by an equilibrium process from othersiloxanes and typically range in viscosity from about 0.01 Pa s to 2500Pa s. Additional particularly useful unsaturated compounds which containsilicon are disclosed in U.S. Pat. No. 4,916,169 (Boardman et al.) whichis herein incorporated by reference. The preferred molecular weight ofthe polysiloxane often depends upon the desired viscosity of thecomposition prior to crosslinking. In general, as the molecular weightis increased the viscosity of the uncrosslinked composition increasescorrespondingly. For uses as molding compositions, the average value ofn preferably is between 10 and 6000. More preferably the average valueof n is between 50 and 2000, and most preferably the average value of nis between 100 and 1000. Mixtures of more than one molecular weight maylikewise be utilized.

The groups R¹ and R² of formula (F1) represent the "terminal" portionsof the polymer chain and are often the sites for the attachment offunctional groups, i.e., groups which participate in the crosslinkingreaction. It is also contemplated that one or more sites depicted informula (F1) as having non-functional methyl groups might insteadcontain a functional group and that R¹ and/or R² then may comprise anon-functional group such as a methyl group or another monovalenthydrocarbyl or halogenated monovalent hydrocarbyl group as listed below.Therefore, formula (F1) is intended merely to illustrate a "typical"polysiloxane polymer with terminal functional groups. The site ofattachment of the two or more functional groups may be varied as desiredand is not believed presently to be of essential importance to thepractice of the present invention. The two or more functional groups arein general unsaturated aliphatic groups having 2 to 20 carbon atoms,such as alkenyl groups including vinyl, allyl, butenyl, propenyl,isopropenyl, and hexenyl groups or cycloalkenyl groups includingcyclohexenyl, cyclopentenyl, cycloheptenyl and cyclooctenyl groups. Apreferred unsaturated aliphatic group is vinyl. Most preferably, both R¹and R² are vinyl groups and are located in terminal positions asdepicted in (F1).

When special properties are needed, other non-functional monovalenthydrocarbyl and halogenated monovalent hydrocarbyl groups may besubstituted for the methyl groups of formula (F1). For example, alkylgroups having 1 to 18 carbon atoms, e.g., methyl, ethyl, propyl, butyl,hexyl, dodecyl, octyl, and octadecyl; cycloalkyl groups having 5 to 7ring carbon atoms, e.g., cyclohexyl and cycloheptyl; aryl groups having6 to 18 carbon atoms, e.g., phenyl, naphthyl, tolyl, xylyl; aralkylgroups including benzyl, β-phenylpropyl, β-phenylethyl, andnaphthylmethyl; alkoxy groups having 0 to 18 carbon atoms such ashydroxy, methoxy, ethoxy, and dodecyloxy; and halo-substitutedhydrocarbon groups such as dibromophenyl, chloromethyl,3,3,3-trifluoropropyl and chlorophenyl may be employed in place of allor some of the methyl groups of formula (F1).

Another compound useful in this invention is a branched polysiloxanehaving the general formula: ##STR3## wherein each R¹ is a functionalgroup or a nonfunctional group as defined above and wherein at least twobut preferably not more than one-half of all the R¹ groups in thesiloxane are functional groups, m represents 0, 1, 2, or 3, and nrepresents a number having an average value from 1 to about 10,000. Itis understood that compounds containing more than one branch point asdepicted in (F1.1) may be employed.

A particularly interesting class of siloxane polymers useful as suitableethylenic compounds in this invention and which contain thefunctionality described in F1.1. are the MQ resins. These polymerscontain tetrafunctional SiO_(4/2) (Q units) and R^(a) R^(b) R^(c)SiO_(1/2) (M units) where the R^(a), R^(b), and R^(c) are vinyl, methyl,phenyl, ethyl, hydroxy, or hydrogen. MQ resins where R^(a) and R^(b) aremethyl and Rc is vinyl are most suitable for use as ethylenic compoundsin this invention. Typically these would not be used as the onlyethylenic compound in the formulation, but rather in combination withother ethylenic compounds, especially the vinyl terminatedpolydimethylsiloxane polymers shown in F1 where R¹ and R² are vinyl. Theuse of certain of these polymers in dental impression materials isdisclosed in U.S. Pat. No. 5,403,885 and in the international patentapplication WO 93/17654.

The preferred amount of the polysiloxane component will vary dependingupon the desired physical properties of the silicone composition (suchas the desired uncured viscosity, cured hardness, etc.). In part due tothe wide range of acceptable molecular weights for the polymer componentand the many types of adjuvants which may be added to the polymer thisamount will vary widely. The presently preferred amount of polymercomponent is between 5% and 99% by weight. More preferably the polymercomponent is between 20% and 90% by weight. Most preferably the polymercomponent is between 20% and 80% by weight.

The crosslinker component contains at least two silicon-hydrogenlinkages and can be a polymeric compound or a compound that is notpolymeric. These compounds are well known in the art and are disclosed,for example in U.S. Pat. Nos. 3,159,662 to Ashby; 3,220,972 toLamoreaux; and 3,410,886 to Joy which are herein incorporated byreference.

Some classes of compounds having at least two silicon-bonded hydrogenatoms which can be used in the invention are:

(a) organohydrosilanes having the empirical formula,

    (H).sub.a (R.sup.3).sub.b Si.sub.c                         (F 2)

wherein each R³ can be the same or different and represents an organicgroup, preferably selected from the group consisting of monovalenthydrocarbyl groups, monovalent alkoxy hydrocarbyl groups and halogenatedmonovalent hydrocarbyl groups, c represents an integer having a value atleast 1, a represents an integer having a value at least 2, and the sumof a and b equals the sum of 2 and two times c;

(b) organohydrocyclopolysiloxanes having the empirical formula,

    H.sub.d R.sup.3.sub.e (SiO).sub.f                          (F 3)

wherein R³ is as defined above, f represents an integer having a valuefrom 3 to 18, d represents an integer having a value at least 2 andpreferably less than or equal to f, and the sum of d and e equals twotimes f; and

(c) organohydropolysiloxane polymers or copolymers having the empiricalformula,

    (H).sub.g (R.sup.3).sub.h Si.sub.j O.sub.(j-1)             (F 4)

wherein R³ is as defined above, j represents an integer having a valuefrom 2 to 10,000, g represents an integer having a value at least 2 andless than or equal to j, and the sum of g and h equals the sum of 2 andtwo times j.

Among the groups represented by R³ include, for example, straight-chainand branched alkyl groups having 1 to 18 carbon atoms, e.g., methyl,ethyl, propyl, butyl, hexyl, dodecyl, octyl, and octadecyl, cycloalkylgroups having 5 to 8 ring carbon atoms, e.g., cyclohexyl and cyclooctyl,aryl, aralkyl, and alkaryl groups having 6 to 18 carbon atoms, e.g.,phenyl, naphthyl, tolyl, xylyl, benzyl and phenylethyl, andhalo-substituted groups thereof, e.g., chloromethyl, chlorophenyl, anddibromophenyl. Preferably, the R³ group includes methyl and phenyl. TheR³ group can also be an unsaturated aliphatic group having 2 to 20carbon atoms, such as alkenyl or cycloalkenyl, e.g., vinyl, allyl andcyclohexenyl. When the R³ group is a group with aliphatic unsaturation,the silicon compound containing silicon-hydrogen linkages can be reactedwith itself to form a polymer.

Another compound having silicon-bonded hydrogen useful in this inventionis a branched organohydropolysiloxane having the general formula:##STR4## wherein each R⁴ is as defined above for R³ and wherein at leasttwo but preferably not more than one-half of all the R⁴ groups in thesiloxane being hydrogen, m represents 0, 1, 2, or 3, and n represents anumber having an average value from 1 to about 10,000. It is understoodthat compounds containing more than one branch point as depicted in (F5)may be employed.

Also useful in the present invention as compounds containing amultiplicity of silicon-bonded-hydrogen groups and which contain thefunctionality described in (F5) are the MQ resins. These polymerscontain tetrafunctional SiO_(4/2) (Q units) and R^(d) R^(e) R^(f)SiO_(1/2) (M units) where the R^(d), R^(e), and R^(r) are vinyl, methyl,phenyl, ethyl, hydroxy, or hydrogen. MQ resins where R^(d) and R^(e) aremethyl and R^(f) is hydrogen are most suitable for use as ethyleniccompounds in this invention. Typically these would not be used as theonly crosslinker component in the formulation, but rather in combinationwith other crosslinker components, especially theorganohydropolysiloxane copolymers shown in (F4).

The amount of the crosslinker component should be sufficient to providethe desired degree of crosslinking of the silicone composition. In partdue to the wide range of acceptable molecular weights for the polymercomponent and/or the crosslinker component, it is presently believedthat this amount is best described in terms of the ratio of SiH groupsto functional (e.g., vinyl) groups in the composition. The presentlypreferred ratio of SiH groups to functional groups ("SiH:F") is between1:1 and 20:1. More preferably the SiH:F ratio is between 1:1 and 10:1.Most preferably the SiH:F ratio is between 1.3:1 and 4:1. The presentlypreferred amount of crosslinker component is between 0.2% and 90% byweight. More preferably the crosslinker component is between 0.2% and20% by weight. Most preferably the crosslinker component is between 0.2%and 10% by weight.

Suitable hydrosilation catalysts for use in the present inventioninclude those compounds which promote or facilitate the additionreaction between the ethylenic groups and the silicon-bonded-hydrogengroups. Examples of suitable catalysts include platinum or platinumcompound catalysts exemplified by chloroplatinic acid, a complex ofchloroplatinic acid and an alcohol, a complex of platinum and an olefin,a complex of platinum and a ketone, a complex of platinum and avinylsiloxane, colloidal platinum, a complex of colloidal platinum and avinylsiloxane etc., palladium or palladium compound catalystsexemplified by tetrakis (triphenylphosphine) palladium, a mixture ofpalladium black and triphenylphosphine, etc.; or rhodium or rhodiumcompound catalysts. Also suitable for use in the present invention areradiation activated hydrosilation catalysts. For example, one mayemploy: (η⁴ -cyclooctadiene)diarylplatinum complexes (as described inU.S. Pat. No. 4,530,879, Drahnak, which is herein incorporated byreference); (η⁵ -cyclopentadienyl)trialkylplatinum complexes (asdescribed in U.S. Pat. No. 4,510,094, Drahnak, which is hereinincorporated by reference); or (η⁵-cyclopentadienyl)tri(σ-aliphatic)-platinum complexes and a sensitizerthat is capable of absorbing visible light (as described in U.S. Pat.No. 4,916,169, Boardman et al., which is herein incorporated byreference) with traditional vinylsiloxane polymers and crosslinkers.Platinum or platinum compound catalysts are presently preferred.Alternatively, Pt(II) beta-diketonate complexes as disclosed in U.S.Pat. No. 5,145,886 or the photohydrosilation catalyst systems describedin U.S. patent application Ser. Nos. 07/626,904 and 07/627,009 aresuitable for use in the present invention, both pending.

For dental molding compositions, "Karstedt" type catalysts as describedbelow are presently most preferred. Karstedt platinum catalysts aredescribed in U.S. Pat. Nos. 3.715,334, 3,775,452 and 3,814,730 which areherein incorporated by reference. In general, to produce a Karstedtcatalyst, there must be utilized (A) platinum halide, and (B) acomplexing material in the form of an unsaturated organosilicon materialselected from:

(a) unsaturated silanes having the empirical formula,

    R.sub.a R'.sub.b Si.sub.c X.sub.z                          (F 6)

where R is free of aliphatic unsaturation and selected from monovalenthydrocarbon radicals, R' is selected from monovalent aliphaticallyunsaturated hydrocarbon radicals, X is a hydrolyzable radical, c is aninteger having an average value of at least 1, b is an integer having anaverage value greater than or equal to 2, and the sum of a plus b plus zequals the sum of 2 and two times c for a linear or branched silane andthe sum of a plus b plus z equals two times c for a cyclic silane;

(b) unsaturated linear or branched siloxanes of the empirical formula,

    R.sub.d R'.sub.e Si.sub.f O.sub.(f-1)                      (F 7)

where R and R' are as defined above, f is an integer having an averagevalue of between 2 and 10,000, e is an integer having an average valuegreater than or equal to 2 and the sum of d and e equals the sum of 2and two times f; and

(c) unsaturated cyclic siloxanes of the empirical formula,

    R.sub.d R'.sub.e Si.sub.f O.sub.f                          (F 8)

where R and R' are as defined above, e is an integer having an averagevalue greater than or equal to 2, f is an integer having an averagevalue from 3 to 18, and the sum of d and e equals two times f.

A Karstedt catalyst can be made by (1) effecting contact between anunsaturated organosilicon material as defined by formula (F6), (F7) or(F8) above, and a platinum halide to provide for the production of amixture having a concentration of available inorganic halogen, (2)treating the resulting mixture of (1) to effect the removal of availableinorganic halogen, and (3) recovering from (2), a platinum-siloxanecomplex having available inorganic halogen of less than about 0.1 gramatoms of halogen per gram atom of platinum. Preferably the complex issubstantially halogen free. As used herein, the term "availableinorganic halogen," will designate halogen that can be detected by amodification of ASTM designation D-1821-63 for "Inorganic Chloride." Theprocedure is substantially as described, except there is utilized inplace of acetone a mixture of glacial acetic acid and acetone. Theprocedure employed for determining gram atoms of platinum in theplatinum-siloxane complexes was Atomic Absorption Spectroscopy. Forexample, the method of R. Dockyer and G. F. Hames, Analyst, 84, 385(1959).

Radicals included by R in formulas F6, F7, and F8 are, for example,alkyl radicals such as methyl, ethyl, propyl, isobutyl, 2-ethylhexyl,dodecyl, etc.; cycloalkyl radicals such as cyclohexyl, cycloheptyl,etc.; aryl and alkaryl radicals such as phenyl, naphthyl, tolyl, xylyl,and the like; aralkyl radicals such as benzyl, tolylethyl, phenylpropyl,etc. Radicals included by R' in formulas F6, F7 and F8 are, for example,aliphatically unsaturated radicals such as ethynyl, 2-propynyl, etc.;vinyl, allyl, 10-undecenyl, and cycloalkenyl radicals, such ascyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and the like.

Unsaturated silanes included by formula (F6) are, for example,tetravinylsilane, triallylmethylsilane, divinyldimethylsilane,trivinylphenylsilane, divinylmethylphenylsilane,divinylmethylethoxysilane, divinylmethylacetoxysilane, and the like.

Included by the unsaturated siloxanes of formula (F7) are, for example,disiloxanes of the formula,

    R.sub.g R'.sub.h SiOSir'.sub.h' R.sub.g'                   (F 9)

where R, R', are as defined above, the sum of h and h' is an integerwith a value of at least two; the sum of g and h is equal to 3; and thesum of g' and h' is equal to 3. For example, there are included asdisiloxanes of formula (F9), 1,1-divinyltetramethyldisiloxane,1,3-divinyltetramethyldisiloxane, hexavinyldisiloxane,1,1,3-trivinyltriethyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane,1,3-divinyl,-1,3-dimethyl,-1,3-diphenyldisiloxane, etc.

There are also included by the unsaturated siloxanes of formula (F8),cyclopolysiloxanes. For example, there is included1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane,1,3,5,7-tetraallyl-1,3,5,7-tetraphenylcyclotetrasiloxane,1,3-divinyloctamethylcyclopentasiloxane, etc.

Preferably the above-described platinum-siloxane complexes of platinumand organosiloxanes of formula (F7) and (F8), are made in accordancewith the practice of the invention, as previously described, utilizing aplatinum halide, and an unsaturated linear, branched or cyclic siloxaneof formula (F7) or (F8) having at least one structural unit of theformula, ##STR5## where the unsatisfied valences ("Si═") of the abovestructural unit can be satisfied by R, R' and oxygen radicals and whereR and R' are as previously defined. Most preferably R' is a vinyl group.

The platinum halides which can be employed in the practice of theinvention are, for example, H₂ PtCl₆.nH₂ O and metal salts such asNaHPtCl₆.nH₂ O, KHPtCl₆.nH₂ O, Na₂ PtCl₆.nH₂ O, K₂ PtCl₆.nH₂ O. Inaddition, PtCl₄.nH₂ O and platinous type halides such as PtCl₂, Na₂PtCl₄.nH₂ O, H₂ PtCl₄.nH₂ O, NaHPtCl₄.nH₂ O, KHPtCl₄.nH₂ O, K₂ PtBr₄ andplatinum halide complexes with aliphatic hydrocarbon as taught in AshbyPats. 3,159,601 and 3,159,662, for example [(CH₂ ═CH₂).PtCl₂ ]₂ ;(PtCl₂.C₃ H₆)₂, etc. may be employed. Other platinum halides which canbe utilized are shown by Lamoreaux Pat. 3,220,972, such as the reactionproduct of chloroplatinic acid hexahydrate and octyl alcohol, etc.

The amount of the platinum complex component should be sufficient toprovide the desired degree of crosslinking of the silicone compositionwithin a reasonable time. In part due to the wide range of acceptablemolecular weights for the polymer component, it is presently believedthat this amount is best described in terms of the ratio of Pt atoms tofunctional groups in the composition. The presently preferred ratio ofPt atoms to functional groups ("Pt:V") is between 1:2 and 1:2000. Morepreferably the Pt:V ratio is between 1:10 and 1:1000. Most preferablythe Pt:V ratio is between 1:30 and 1:500. Preferably, the catalyst ispresent in an amount from about 5 to about 1000 parts by weight per1,000,000 parts by weight of the total composition, more preferably fromabout 20 to 500 parts by weight per 1,000,000 parts by weight of thetotal composition.

A "cure-indicating dye" is added to the curable composition to provide avisual indication of the extent of the hydrosilation reaction (e.g.,extent of the crosslinking reaction). The cure-indicating dye exhibits acolor change in the presence of a silicon-bonded-hydrogen compound and aprecious metal hydrosilation catalyst and is characterized in a curablecomposition by having a first color before the cure reaction is effectedand a second color after the cure reaction has been effected. Here"color" is taken to include visible fluorescence. The first color andsecond color are different and may be observed readily in thecomposition using the naked eye or a suitable instrument such as aspectrophotometer, colorimeter, or fluorimeter. Preferably, thedifference in color may be observed readily using the naked eye bycomparing the composition's second color to a reference color standard(e.g., a printed card, printed label or colored plastic part such as acolored plastic dental impression tray) that approximates either thecomposition's first color (i.e., a color mis-match is observed) or, morepreferably, the composition's second color (i.e., a color match isobserved). Similarly, the composition's second color may be compared toanother composition that approximates the first composition's secondcolor. For example, a commonly employed dental impression techniqueinvolves a "two-phase" system comprising a "putty" material and aseparate "wash" material. In the present invention, one may choose toadd a cure-indicating dye to either or both materials. For example, oneof these materials (e.g., the wash) could contain a cure-indicating dyeand change color upon curing to match the unchanging color of the othermaterial (e.g., the putty). Alternatively, the putty and wash could eachcontain a different cure-indicating dye (thus having different initialcolors) and change color upon curing to "match" each other. Morepreferably, the color change is pronounced such that the color changemay be readily "recognized" by an observer even without the need for areference color standard.

The dye's first color (e.g., before the cure reaction is effected) istypically fairly intense and may occupy virtually any visibly observablechroma. The dye's second color (i.e., after the cure reaction iseffected) may be either a different color or be no color at all (i.e.,the cure-indicating dye has been "bleached" to a colorless state and thenatural color of the composition without the dye is observed). It isalso expected that a suitable cure-indicating dye for use in the presentinvention may change from a visibly colorless state to a colored dye asa result of the curing reaction. For example, a colorless dye havingstrong near-infrared absorption may change to a visibly light absorbingdye, etc. Change of fluorescence color or intensity is another option.

The color change of this invention is correlatable with the extent ofthe hydrosilation reaction (e.g., correlatable with the extent of cureof the curable composition). The rate of color change can be adjusteddepending on the particular cure-indicating dye employed, the amount ofcure-indicating dye employed (relative to the other active components ofthe composition), and/or whether other indicator adjuvants are presentin the composition. Similarly, the time at which the color change occursrelative to the crosslinking reaction can be adjusted. As will bedemonstrated below this makes it possible to provide compositions whichreproducibly exhibit a color change at virtually any desired point inthe cure reaction.

Two-part curable compositions typically are formulated to be "shelfstable" (i.e., storage stable) for relatively long periods of time priorto being combined into one part. This may be accomplished, for example,by separating the catalyst component from the crosslinker component. Thecuring reaction is begun by mixing the two parts together. This may bedone manually (e.g., by hand mixing or kneading the two pastes togetheruntil one homogeneous paste is formed) or by employing a static mixer orother mechanical mixer.

The working time of a two-part material refers to the time between theinitiation of the setting reaction, e.g., when the vinyl-containingorganopolysiloxane, the organohydropolysiloxane, and the platinumcatalyst are mixed together, and the time the setting reaction hasproceeded to the point at which it is no longer practical to performfurther physical work upon the system, e.g., reform it, for its intendedpurpose. When the reaction has proceeded to this later point thematerial is said to have reached its gel point. The working timepreferably provides enough time comfortably to mix and place thecomposition into its desired form but not so much time that the settingtime is delayed unreasonably. For dental impression compositions theworking time under conditions of use is preferably greater than 30seconds, more preferably greater than 1 minute and most preferablygreater than 2 minutes. Longer working times may also be acceptable. Anindication of the end of the working time may be accomplished byadjusting the timing of the color change to coincide with or justprecede the onset of the gel point of the material. This indication isvery useful as it serves to warn the user visually of the onset of thegel and the finish of the working time. If desired, this color changecan be adjusted to occur a few moments before this gel point, thusproviding a longer warning period and allowing the user time to hurry,if need be, to finish the procedure or operation.

The setting time of an impression material refers to the time at whichsufficient curing has occurred to allow removal of the siliconeimpression material from the surface being replicated without causingpermanent deformation of said silicone material. The setting time of acoating refers to the time at which sufficient curing has occurred toallow the coating to be further processed or otherwise used for itsintended purpose without physical damage to the coating. For animpression material, the setting time may be approximated by measuringthe torque of the reacting composition by means of an oscillatoryrheometer held at the desired temperature (e.g., held at the sametemperature as would be encountered in use). As the material cures thetorque value rises. When the torque reaches a maximum value the materialis said to be fully set. For practical use of dental impressioncompositions, and for purposes of this invention, the point in timewhere the torque reaches 90 percent of its maximal value is defined asthe setting time (this time is also referred to as "T90"). In general,shorter setting times are preferred over longer setting times. Fordental impression compositions the setting time is preferably less than10 minutes. More preferably the setting time is less than the sum of 5minutes plus the working time. Most preferably the setting time is justlonger than the desired working time. An indication of the arrival ofthe set time may be accomplished by adjusting the timing of the colorchange to coincide with or come just after the set time of the material.This visual indication is very useful as it serves to prompt the user ofthe achievement of the set and prevents undesirable and inadvertentremoval or distortion of the material prior to its being completely set.If desired, this color change can be adjusted to occur a few momentsafter the set time, thus providing a safety margin.

For dental impression materials a cast of the dental tissue is oftenfabricated by pouring a liquid plaster, wax, or other hardenablematerial (e.g., a curable liquid epoxy material) into the setimpression. Unfortunately, the surface of the cast can be marred if theimpression material evolves gas during the time that the castingmaterial is in contact with the impression and is itself hardening. Theevolved gas can form bubbles on the surface of the casting material anddisplace the casting material from the surface being replicated forminga permanent defect in the cast. To avoid this problem it is customary todelay the pouring of the cast until well after the impression materialis considered fully set. This allows the impression material tocompletely de-gas before the casting material is poured into theimpression. An indication of the arrival of this desired "pour time"might be accomplished by adjusting the timing of the color change tocoincide with or come just after the end of deleterious gas evolution.This visual indication would be very useful as it would serve to promptthe user when the impression is safe to "pour up" and would preventundesirable and inadvertent pouring of the casting material prior tocomplete gas evolution from the impression material.

In addition to monitoring the over-all cure reaction of a curablecomposition, the cure-indicating dye can also be used to indicatesmaller localized regions on a curable composition where incompletecuring may have taken place. A recurring problem in dental impressionmaking involves localized "poisioning" of the impression material whichcan delay or prevent curing of the material. This can occur, forexample, when a "poison" is transferred from the surface beingreplicated to the impression material. This can happen when the dentistor assistant touches the surface of the tooth being impressioned with acontaminant and the contaminant then contacts the impression material. Acommon source of contaminant is a latex glove worn by the health careprovider. The contaminants found on many latex gloves can delay orinhibit the cure of the silicone impression material. Another commonsource of contaminant includes acrylate-based and methacrylate-baseddental composites and adhesives. Unfortunately, the transfer of acontaminant to the tooth surface cannot always be observed readily bythe dentist. Likewise, localized defects caused by such contaminants maynot be observed readily by looking at impressions made from traditionalimpression materials. However, if this localized delay occurs at acritical area the impression may be mined, i.e., by not accuratelyrepresenting the tooth being impressed, thereby causing a defectiveappliance (e.g., crown) to be produced. By using the cure-indicating dyeof the present invention the health care provider can observeimmediately any areas of the impression material that were contaminated.This can be accomplished visually by observing the surface of theimpression material after it has been taken out of the mouth. If anyareas exhibit unchanged color (or not completely changed color withinabout 30 seconds) then the impression may be bad and should be retaken.This saves the expense of making a crown or appliance that does not fitproperly. In addition, the dentist thereby can detect recurring problemsin his or her technique and adjust accordingly. Notably, certain regionsof the impression may, even under optimal conditions, change color laterthan other regions. For example, the surface of a tooth is somewhatcooler than the surrounding gum tissue. This can cause the impressionmaterial adjacent to the tooth to set more slowly than the impressionmaterial adjacent to the gum tissue. This time delay is normally veryshort.

For coating compositions the cure-indicating dye may be employed tomonitor (on-line or off-line) the coating process. Extent of cure,uniformity of cure, or overall coating quality may be monitoredeffectively by observing the composition's color. Preferably, ableaching reaction will be employed in order to permit more thoroughinspection and/or be inconspicuous for the intended use. For example, ifone or more regions of the coating are not adequately cured (e.g., afterbeing exposed to heat or visible or UV radiation) the color of thecure-indicating dye will remain unchanged. In addition, incompletecoatings may be similarly detected.

As previously mentioned, the cure-indicating dye provides a visualindication of the extent of cure of a curable composition. The colorchange of a dye may be observed using a suitable detection device suchas an instrument (e.g., a spectrophotometer, fluorimeter or colorimeter)or the human eye. Depending on the intended use of the curablecomposition one or another detection device might be preferred. Forexample, for dental impression materials it is believed that observationof the color change will ordinarily be made by the naked eye (oroptionally with assistance of corrective eyewear). For coatingcompositions (e.g., coatings on films used as release liners) it isbelieved that an off-line or on-line instrument can be utilizedeffectively to monitor the color change, and thus the cure, of thecoating.

The amount of color change exhibited by the dye in a given compositionneed be only that amount of change that can be accurately measured orrecognized by the detection device. It is understood that an instrumentsuch as a spectrophotometer can detect fairly small color changesreproducibly. In contrast, the human eye may not notice or "remember"small color changes, especially when lighting is variable, although thehuman eye can detect very small color differences when two colors arecompared directly (e.g., side by side comparison using a referencestandard color). For dental impression materials the amount of colorchange is preferably sufficient that when one compares two colorsside-by-side using the human eye a color difference is observable. Morepreferably, the color difference is readily observable, i.e., thedifference is recognized after just a short observation time. Mostpreferably, the color change is observable without reference to aside-by-side comparison. That is, the observer can detect and recognizea difference between the second color and the "remembered" first colorof the composition.

If desired, the recognition of a color change can be facilitated byproviding a conveniently-located reference first or second colorstandard. The observer can compare the composition's color with thereference first or second color standard. This allows the observer todetect the color change more easily. If the reference standard matchesthe first color of the composition, the observer will detect a smallchange in color of the composition away from the reference first colorstandard. This first observation of a color difference can be used asthe indication point of interest. If the reference standard matches thesecond color of the composition, the observer will be presentedinitially with a contrast in color between the reference standard andthe curable composition (i.e. a color mismatch). This difference willbecome smaller, and preferably eventually disappear, as the compositioncures. When the two colors eventually match the dye will have reachedits second color and the indication point will have been obtained.

The reference standard may be provided, for example, as a separate color"chip" or printed card. This chip or card may be held against the curingcomposition for side-by-side comparison. Alternatively, for conveniencewhen using dental impression materials, the reference standard may beapplied directly to an impression tray (e.g., as a paint or label or asthe natural color of the molded impression tray).

If desired the curable composition may also comprise an additionalcure-indicating dye or dyes (i.e., the composition may comprise two ormore different cure-indicating dyes). The additional cure-indicating dyeor dyes may be used to provide additional indication points or toenhance one indication point. For example, a second cure-indicating dyeand the first cure-indicating dye can together provide a first color tothe curable composition (i.e., before curing has occurred). The firstcure-indicating dye can be tailored to monitor one point in the curereaction (e.g., the extent of working time) and the secondcure-indicating dye can be tailored to monitor a different point in thecure reaction (e.g., the setting time). When the composition reaches thegel point (i.e., the extent of the working time) the firstcure-indicating dye changes color or is bleached. This is observable asa color change in the composition (the composition retains the color ofthe second cure-indicating dye and any remaining color from the firstcure-indicating dye). As the reaction proceeds and the set time isreached, the second cure-indicating dye changes color causing thecomposition to exhibit a third and final color.

In addition, if desired the curable composition may also comprise anadditional non-cure-indicating dye or pigment. The non-cure-indicatingdye or pigment modifies the color of the composition from its naturalstate and may combine with the first color of the cure-indicating dye toprovide a first composition color that differs from both the firstcure-indicating dye color and the natural composition color. Forexample, it is well known that a blue dye and a yellow dye will providea green color. If the blue dye is a cure-indicating dye (e.g., a dyethat changes from blue to colorless when the indication point isreached) and the yellow dye is a non-cure-indicating dye, thecomposition will have a green color initially and at the point ofinterest change to a yellow color. Other combinations of colors can beemployed, depending on the desired color change and/or desired initialor final color.

The cure-indicating dye should be present in an amount sufficient toprovide a visual indication of the extent of the hydrosilation reaction.The amount of cure-indicating dye needed will depend on a number offactors including the natural color of the composition and the desiredamount of color change (e.g., less color change may be needed when thedetector is more sensitive, more color change may be needed when thecolor change is poorly visible). In addition, the amount of dye neededwill also depend on the dye's tinctorial strength. The cure-indicatingdye should have enough tinctorial strength to color the compositioneffectively and provide for the necessary color change. A common measureof tinctorial strength is the dye's "extinction coefficient." Ingeneral, higher extinction coefficient dyes are preferred due to theirgreater contribution per molecule to color. Lower extinction coefficientdyes, while not preferred, may nevertheless be employed, usually atsomewhat higher concentration. Preferred cure-indicating dyes for use inthe present invention have a molar extinction coefficient in the visiblespectrum of at least 1,000M⁻¹ ×cm⁻¹, more preferably at least 10,000M⁻¹×cm⁻¹, and most preferably at least 30,000M⁻¹ ×cm⁻¹. For use in dentalimpression materials, the amount of dye preferably should be asufficient amount such that the dye's contribution to the composition'scolor can be easily observed using the naked eye. Preferred impressionmaterials comprise between 0.0001 and 0.1 weight % cure-indicating dye(based on the total weight of the curable composition and whennormalized to a dye having a molar extinction coefficient of 32,000M⁻¹×cm⁻¹), more preferably between 0.0003 and 0.03 weight % cure-indicatingdye, and most preferably between 0.001 and 0.015 weight %cure-indicating dye. Those skilled in the art of dye chemistry willunderstand that for dyes with a lower molar extinction coefficientcorrespondingly greater amounts of cure-indicating dye will be requiredto achieve the same color intensity as a cure-indicating dye with ahigher molar extinction coefficient. Preferred coating compositionscomprise between 0.0002 and 0.2 weight % cure-indicating dye (based onthe total weight of the coating composition but not including the weightof any volatile solvents that are not present when the coating's coloris to be observed and when normalized to a dye having a molar extinctioncoefficient of 32,000M⁻¹ ×cm⁻¹), more preferably between 0.0006 and 0.06weight % cure-indicating dye, and most preferably between 0.002 and 0.03weight % cure-indicating dye. A maximum effective amount of acure-indicating dye is an amount sufficient to allow visible (or,optionally, near-infrared) radiation to penetrate the coating to itsfull depth and provide a maximal signal consistent with there being ameasurable signal from the entire working depth of the coating. Amountsin excess of an effective amount will tend to absorb all of the visibleradiation in the upper portion of the coating and may provide no usefulsignal from the lower portion to indicate its thickness or extent ofcure. When color is bleached upon cure, it becomes possible to monitorat greater depths. Amounts less than the maximum effective amount may behighly satisfactory or even preferred if it is desired that the coatingweight be directly proportional to the initially measured or the finalsignal.

Preferred cure-indicating dyes change color very rapidly when theindication time (e.g., the working time, setting time, etc.) has beenreached. The time between tile onset of color change and tile completionof the color change is referred to as the "transition time". For dentalimpression materials a "typical" working time is measured in minutes(e.g., 0.5 to 2 minutes). Based on this time frame preferredcure-indicating dyes used to monitor working time change color within aone minute period, more preferably within a 30 second period. Similarly,typical dental impression materials have a set time of 3 to 7 minutes.Based on this time frame preferred cure-indicating dyes used to monitorset time change color within a three minute period, more preferablywithin a two minute period, most preferably within a one minute period.When longer indication times are being monitored, a longer transitiontime (i.e., the time over which the cure indicating dye exhibits achange of color) can be tolerated. For coating compositions, preferredcure-indication dyes change color rapidly and most preferably exhibit acomplete color change prior to the winding of the coated article. Inthis manner an inspection of the coated article may be made "on-line."

In addition to tile above-mentioned requirements, the cure-indicatingdye (which may be a liquid or solid) should be, and preferably is,soluble or dispersible in the composition being colored. A "soluble"cure-indicating dye, as used herein, is a cure-indicating dye that whenmixed with the initial or uncured composition (including any optionalsolubilizing agents, e.g., cosolvents or surfactants, that are presentin the composition) under the desired conditions of use dissolves toform a homogeneous colored mixture. Such conditions of use includetemperature (e.g., over the temperature range encountered during use andcure of the composition), time (e.g., the amount of time the compositionis in the uncured state), and concentration (e.g., the concentration ofcure-indicating dye in the composition). A "dispersible" cure-indicatingdye, as used herein, is a cure-indicating dye that when mixed with thecomposition (including any optional solubilizing agents, e.g.,cosolvents or surfactants, that are present in the composition) underthe desired conditions of use forms a macroscopically homogeneouscolored mixture. The dye may be in the form of very small particlessuspended in the composition, i.e., form a two-phase system where onephase consists of finely divided particles (often in the colloidal sizerange) distributed throughout a bulk substance, the particles being thedisperse or internal phase and the bulk substance the continuous orexternal phase. The dye particle should be small enough that the dyecolors the mixture and is capable of interacting with the composition tochange color as desired. An "insoluble" or "nondispersible" dye proposedfor cure-indication purposes, as used herein, is apotentially-cure-indicating dye that when mixed with the composition(including any optional cosolvents that are present in the composition)under the desired conditions of use forms a macroscopicallyheterogeneous mixture. A macroscopically heterogeneous mixture, as usedherein, includes phase-separated liquid/liquid systems (e.g., oil andwater); two-phase systems comprising a granular or powdery solid phasein a liquid; and two-phase systems comprising a suspension of largeparticles in a liquid, wherein the large particles do not color thecomposition or do not interact with the composition to change color asdesired.

As previously mentioned the composition containing the cure-indicatingdye may optionally comprise one or more suitable cosolvents. Thecosolvents may be employed to facilitate the dissolution or suspensionof the cure-indicating dye and/or other adjuvants in the composition, tofacilitate uniform mixing of the reactants, or to adjust thecomposition's viscosity or flow. Suitable cosolvents for use withsilicone compositions include aromatic hydrocarbons, such as xylene andtoluene, aliphatic hydrocarbons, such as hexane and mineral spirits, andhalogenated hydrocarbons, such as chlorobenzene and trichloroethane. Itis desirable that the solvent be transmissive to visible light. Thecomposition preferably contains less than about 70 weight percentcosolvent, more preferably less than 40 weight percent cosolvent, andmost preferably less than about 10 weight percent cosolvent.

Preferred cure-indicating dyes are soluble or dispersible, morepreferably soluble, in the curable composition without the presence of acosolvent. The solubility or dispersibility of a dye can be adjusted, ifneeded or desired, by several means. For example, an otherwise insolubleor nondispersible dye may be "tethered" to another compound that has thenecessary or desired solubility or dispersibility in the composition.Preferably, the tethered dye molecule will have characteristics of bothcompounds (i.e., the cure-indicating properties of the dye and thesolubility characteristics of the other compound). The attachment ortethering may be covalent or ionic. For example, if ionic tethering isemployed one may associate an otherwise insoluble cationic or anionicdye to a suitably soluble anion or cation, respectively. The tetheringion may be itself attached to the curable polymer. Alternatively, anotherwise insoluble neutral dye may be covalently attached to anothercomponent to render the resulting larger molecule soluble or dispersiblein the composition. Typically this may be done by attaching theinsoluble dye to the molecules of the composition, e.g., attaching thedye to the curable silicone polymer. Of course, one may also attach asoluble dye to the molecules of the composition. This may be desired ina situation where it is important that the dye not "leach out" or"bloom" from the cured composition (e.g., where toxicity orenvironmental issues are of concern).

Suitable cure-indicating dyes are soluble or dispersible, morepreferably soluble, in the curable composition (including any optionalsolubilizing agents, e.g., cosolvents or surfactants, that are presentin the composition) at a concentration sufficient to color thecomposition effectively. Preferably, the cure-indicating dye is solubleor dispersible in the composition at a concentration sufficient to colorthe composition effectively without the need to employ a cosolvent. Morepreferably, the cure-indicating dye is soluble or dispersible at asufficient concentration such that the dye's contribution to thecomposition's color can be observed readily using the naked eye (or fora coating compositions using a suitable detection device).

As previously mentioned, suitable cure-indicating dyes for use in thepresent invention exhibit a color change in the presence of amultiply-silicon-bonded-hydrogen compound, a multiply-ethyleniccompound, and a precious metal hydrosilation catalyst when theaformentioned compounds are allowed to react under the desiredconditions of use (i.e., time, temperature, concentration in thecomposition, etc.). A simple and effective method of testing whether aparticular dye is potentially suitable for use in the present invention(i.e., not yet considering solubility/dispersibility issues) involvesmixing the dye with the following model compounds and observing whetheror not the dye exhibits a color change. This model system differssubstantially from the conditions that occur in a curable composition,since this model system does not undergo a "curing" reaction.Furthermore, and notably, a solvent system is used instead of thepolymer composition of a curable composition. Dyes are evaluatedaccording to the following test method (hereinafter referred to as the"pentamethyldisiloxane test"). First, 500 μg (micrograms) of dye istransferred to a 6 μl clear-glass, screw cap vial. Five hundred μl(microliters) of dichloromethane is then pipetted to the vial, followedby 100 μl of pentamethyldisiloxane. The dye, dichloromethane andpentamethyldisiloxane are mixed until homogeneous. To this solution isadded an effective amount of a "hydrosilation catalyst solution."Suitable hydrosilation catalyst solutions and suitable effective amountsof such catalyst solutions for use in this test include the followingcatalyst solutions: (A) 25 μl of a catalyst solution comprising 25% byweight of a commercially available catalyst (PC075, available fromUnited Chemical Technology, Inc., Bristol, Pa.) in dichloromethane; (B)10 μl of a commercially available catalyst solution (PC072, availablefrom United Chemical Technology, Inc., Bristol, Pa.); or (C) 10 μl of aKarstedt-type catalyst solution in toluene, wherein said catalystcomprises a complex of Pt^(o) and 1.5 equivalents (1.5 g mols per g atomPt) of divinyltetramethyldisiloxane and wherein said solution hasbetween about 2 and 3 weight percent platinum. The United ChemicalTechnology catalyst solutions are further described at page 268 inSilicon Compounds Register and Review--Silicones & Silicon-ContainingPolymers--5th Edition, edited by Roy Anderson, G. L. Larson and CraigSmith, Huls America Inc., Piscataway, N.J., which is herein incorporatedby reference. The Karstedt-type catalyst solution in toluene is furtherdescribed in Preparatory Example 1b and on page 13 of "Aspects of SomeDivinylsiloxane Complexes of Platinum and Rhodium," PhD thesis byNicholas John William Warhurst, University of Sussex, March 1990, whichis herein incorporated by reference. The vial is capped, agitated forapproximately 5 seconds at room temperature (25° C.) and the solutionobserved for color change (e.g., bleaching). Those dyes that exhibited asignificant color change (e.g., bleaching) within 24 hours andpreferably within less than about 10 minutes under these conditions arebelieved to be suitable candidates for use in the present invention(subject to their having the desired solubility or dispersibility in thecomposition as discussed above). To verify that the above test is beingperformed correctly (e.g., that the selected catalyst solution isactive), one may repeat the above test using a dye which has beendemonstrated to bleach under these conditions. For example, dye #2 ofTable 1a is known to bleach in less than about 10 minutes under theseconditions and is a suitable dye for use in this invention. In the eventthat the dye is not soluble in 500 μl of dichloromethane, then one mayeither utilize additional dichloromethane (i.e., sufficient to dissolvethe dye) or utilize a different solvent which is capable of dissolvingthe dye, and which is verified to not interfere with the bleaching ofdye #2 as indicated above.

The amount of color change exhibited by a particular cure-indicating dyemay be measured using a visible light spectrophotometer in conjunctionwith the above test. A small-volume short-path-length cuvette containing500 mg of dye, 500 ml of dichloromethane, and 100 μl ofpentamethyldisiloxane is positioned in the spectrophotometer andmeasured for its absorptivity to visible, near-UV and near IR light. Thepath length (or if necessary the amount of dye) is chosen to provideabsorbance less than 4.0 at λ_(max). The absorbance is compared to thatof a similar solution, but that contains 10 or 25 μl, as appropriate, ofthe previously mentioned catalyst solutions and has been allowed to"bleach" for about 10 minutes as described above). Preferredcure-indicating dyes for use in the present invention exhibit a 10-folddecrease in absorbance (as measured at λ_(max)) when tested in thismanner (i.e., a loss of 90% in absorbance). More preferredcure-indicating dyes for use in the present invention exhibit a 100-folddecrease in absorbance when tested in this manner (i.e., a loss of 99%in absorbance). Most preferred cure-indicating dyes exhibit a 10-fold or100-fold decrease in absorbance in less than about 5 minutes when testedin this manner.

A simple and effective method of establishing approximate timingsignaled by a cure-indicating dye involves mixing the dye with thefollowing model curable composition and observing whether or not the dyeexhibits a color change at or near the time when the model curablecomposition sets, as determined by laboratory testing such asoscillatory rheometry. The model curable composition contains compoundsselected to perform the function of the catalyst, the SiH compound, andthe polymer compound. Dyes are evaluated according to the following testmethod. First, approximately 500 μg of dye is transferred to a 6 mlclear-glass, screw cap vial. One ml of stock composition B1 fromPreparatory Example 2 is transferred to the vial via pipette or dropper,the solution is mixed with a spatula for 3 minutes and the mixture isexamined visually for coloration of the resin and general solubility ofthe dye. If necessary, 1-2 drops (approximately 0.015 to 0.03 gms) ofdichloromethane may be added to promote the solubility of less solubledyes. One ml of stock composition C2 from Preparatory Example 2 istransferred to the vial and mixed with a small stick. The composition isplaced against a white background and examined visually and manually forthe time at which gelation occurs (as evidenced by an increase inviscosity and minimal flow when the vial is inverted) and the time atwhich the color changes. Those dyes that exhibit color change (e.g.,bleaching) within 2 times the gel time are believed to be candidates foruse in the present invention. This procedure may be repeated withvarious types and amounts of additives to adjust the time of colorchange for the intended use.

While not intending to be bound by theory, it is believed presently thatsuitable cure-indicating dyes include those dyes that are reduced (e.g.,catalytically hydrogenated) in the presence of a silicon-bonded-hydrogencompound and a precious metal hydrosilation catalyst when theaformentioned compounds are allowed to react under the desiredconditions of use (i.e., considering time, temperature, concentration inthe composition, etc.). These reactions are exceedingly difficult tostudy in detail. It is presently believed that the reduction of thecure-indicating dye affects the chromophore of the dye, interruptingconjugation and thereby altering its apparent color. For example, it isknown to the inventors that2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-oneis reduced to2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]amino]-1-phenol in thepresence of the silicon-bonded-hydrogen compound acting as a source ofhydrogen, and a precious metal hydrosilation catalyst.

For dyes capable of cure-indication, it is believed that there is acompetition for different reaction pathways involving theorganohydropolysiloxane crosslinker. In a first pathway the SiH groupson the crosslinker react with the unsaturated groups on theorganosiloxane, catalyzed by the Pt catalyst, to effect hydrosilation.In a second pathway the SiH groups on the crosslinker react with otherSiH groups (or with sources of protons such as acids), also catalyzed bythe Pt catalyst, to generate hydrogen gas. In general the first pathwayis dominant when the three ingredients (e.g., vinyl polymer,organohydropolysiloxane crosslinker, and Pt catalyst) are first mixed.As the reaction proceeds the concentration of unsaturated groups fallsdramatically relative to the generally more abundant SiH groups and thereaction pathway begins to favor hydrogen gas production. The hydrogengas, in the presence of Pt catalyst, is believed to reduce (by catalytichydrogenation) certain (and perhaps all) of the cure-indicating dyes ofthe present invention, resulting in a change in color of the dye. It isalso believed that the propensity of the dye to be reduced has a strongimpact on the timing of the color change (i.e., in relation to thetiming of the hydrosilation cure reaction). Dyes that are very easilyreduced (e.g., as indicated by cyclic voltammetry) will generally reactand change color sooner than dyes which are less easily reduced. Otherfactors such as the ratio between SiH groups and unsaturated groupsand/or the presence of adjuvants affect the relative rates ofhydrosilation and hydrogen production. In this way the color change maybe adjusted to coincide with the desired point in the curing reaction.

Suitable dyes for use in the present invention may be classified bytheir reducible chromophore into several generic groups. Representativeof these groups include indoaniline dyes, indophenol dyes, quinonemonoimine dyes, quinone diimine dyes, cyanine dyes, merocyanine dyes (ahybrid of a true cyanine dye and a true oxonol dye), cyclohexadienonedyes, iminocyclohexadienone dyes, imidazolylidinecyclohexadienone dyes,dihydronaphthalenone dyes, iminodihydronaphthalenone dyes,imidazolylidinedihydronaphthalenone dyes, cyclohexadienimine dyes,sulfone dyes including: aryl substituted bistrifluoromethylsulfonylhexatrienyl dyes, aryl substituted bis(trifluoromethylsulfonyl)butadienyl dyes, aryl substituted bis(fluorosulfonyl)hexatrienyl dyes, and aryl substituted bis(fluorosulfonyl)butadienyl dyes, oxazolone dyes, and ionic dyesincluding cationic dyes, anionic (e.g., oxonol) dyes, and betaine dyes.By "cationic dye" is meant an ionic dye having a cationic chromophore.By "anionic dye" is meant an ionic dye having an anionic chromophore.Neutral azo dyes and anthraquinone dyes, which do not pass thepentamethyldisiloxane test previously described, are not now believed tobe suitable for use in the present invention.

As is well understood in this area, substitution is not only tolerated,but is often advisable. As a means of simplifying the discussion andrecitation of certain terminology used throughout this document, theterms "group" and "moiety" are used to differentiate between chemicalspecies that allow for substitution, or which may be substituted("group"), and those which do not so allow or may not be so substituted.Thus when the term "group" is used to describe a chemical substituent,the described chemical material includes the basic group and that groupwith conventional substitution. Where the term "moiety" is used todescribe a chemical Compound or substituent, only an unsubstitutedchemical material is intended to be included. For example, the phrase"alkyl group" is intended to include not only pure open-chain, branched,and cyclic hydrocarbon alkyl substituents, such as methyl, ethyl,propyl, isopropyl, tert-butyl, cyclohexyl, adamantyl, octadecyl, and thelike, but also alkyl substituents bearing further substituents known inthe art (e.g., silicon substituted, oxygen substituted, etc.). On theother hand, the phrase "alkyl moiety" is limited to the inclusion ofonly pure open-chain, branched and cyclic hydrocarbon alkylsubstituents, such as methyl, ethyl, propyl, isopropyl, tert-butyl,cyclohexyl, adamantyl, octadecyl, and the like. As used herein, a"hydrocarbyl-containing group" is intended to include not only pureopen-chain, branched, and cyclic hydrocarbyl substituents but alsohydrocarbyl substituents which bear further substituents known in theart (e.g., silicon substituted, oxygen substituted, etc.) and/or whichare linked to the basic compound by means of a heteroatom other thancarbon (e.g., sulfur, oxygen, nitrogen and silicon).

One class of particularly suitable dyes may be represented by thefollowing general formula (F11): ##STR6## wherein: each R¹, R², R³, andR⁴ group is independently hydrogen, halogen, a hydrocarbyl-containinggroup, or a heterocyclic group, preferably each R¹, R², R³, and R⁴ groupis independently selected from the group consisting of: hydrogen,halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆-C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²), and wherein R¹ and R²or R³ and R⁴ may be connected to form a saturated or unsaturated ring,for example, R³ and R⁴ may be joined by or be a --C₄ H₄ --, --(CH₂)₃ --,or --C₃ H₃ N-- moiety; more preferably each R¹, R², R³, and R⁴ group isindependently selected from the group consisting of: hydrogen, halogen,a C₁ -C₁₀ alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl,a C₂ -C₁₀ alkenyl, and a C₁ -C₁₀ alkylamino, and wherein R¹ and R² or R³and R⁴ groups may be connected to form a saturated or unsaturated 5 to 8member ring, for example, R³ and R⁴ may be joined by a --C₄ H₄ -- or--C₃ H₃ N-- moiety; most preferably each R¹, R², R³, and R⁴ group isindependently selected from the group consisting of: hydrogen, methyl,ethyl, propyl, tert.-butyl, methoxy, ethoxy, isopropoxy, tert.-butoxy, aC₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₂ -C₁₀ alkenyl, a C₁ -C₁₀alkylamino, chlorine, and bromine, and wherein R³ and R⁴ may be joinedby a --C₄ H₄ -- or --C₃ H₃ N-- moiety;

A is O, S, or NR²², wherein

R²² is hydrogen, a hydrocarbyl-containing group, or a heterocyclicgroup, preferably R²² is a group selected from the group consisting of:hydrogen, a C₁ -C₂₀ alkyl, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₂-C₁₈ alkenyl, a C₆ -C₁₈ arylamino, and substituted sulfonyl; morepreferably R²² is selected from the group consisting of hydrogen and--SO₂ C₆ H₅ ; and

B is any group capable of providing extended conjugation therebyrendering the dye capable of absorbing visible, near-UV, ornear-infrared radiation including groups of formula D, E, F, H, or J,wherein

D is represented by formula (F12): ##STR7## wherein: each R⁵, R⁶, R⁷,R⁸, and R⁹ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group, preferably eachR⁵, R⁶, R⁷, R⁸, and R⁹ group is independently selected from the groupconsisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, aC₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl,a C₂ -C₂₀ di(hydrocarbyl)amino, morpholino, and alkylamido and whereinany two adjacent R⁵, R⁶, R⁷, R⁸, and R⁹ groups may be connected to forma saturated or unsaturated ring, for example, R⁵ and R⁶ or R⁶ and R⁷ maybe joined by or be a --C₄ H₄ -- or --C₃ H₃ N-- moiety; more preferablyeach R⁵, R⁶, R⁷, R⁸ and R⁹ group is independently selected from thegroup consisting of: hydrogen, halogen, a C₁ -C₁₀ alkyl, a C₁ -C₁₀alkoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₆ -C₁₈ aryloxy, a C₂-C₁₀ alkenyl, a C₁ -C₁₀ alkylamino, a C₆ -C₁₈ arylamino, a C₂ -C₂₀di(hydrocarbyl)amino, morpholino, and alkylamido and wherein any twoadjacent R⁵, R⁶, R⁷, R⁸, and R⁹ groups may be connected to form asaturated or unsaturated 5 or 6 member ring; most preferably each R⁵,R⁶, R⁷, R⁸ and R⁹ group is independently selected from the groupconsisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy,propoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, benzyloxy, naphthyloxy, aC₂ -C₁₀ alkenyl, N,N-dialkylamino, N-alkyl-N-arylamino, --N(Et)[((CH₃)₃C)₂ (CH₃)₁ SiOCH₂ CH₂ ], chlorine, bromine, morpholino, and alkylamidoand wherein R⁵ and R⁶ or R⁶ and R⁷ may be joined by or be a --C₄ H₄ --,--(CH₂)₃ --, or --C₃ H₃ N-- moiety;

E is represented by formula (F13): ##STR8## wherein: X¹ is C(R¹²)₂, S,NR¹², or O, more preferably X¹ is S or O, most preferably X¹ is S;

X² is C(R¹²)₂, S, NR¹², or O, more preferably X² is C(R¹²)₂ or NR¹²,most preferably X² is NR¹² ; and

each R¹⁰, R¹¹ and R¹² group is independently hydrogen, ahydrocarbyl-containing group, or a heterocyclic group, preferably eachR¹⁰, R¹¹ and R¹² group is independently selected from the groupconsisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, aC₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, and wherein R¹⁰ and R¹¹ may be connected to formor be a ring; more preferably each R¹⁰, R¹¹ and R¹² group isindependently selected from the group consisting of: hydrogen, a C₁ -C₁₀alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₂ -C₁₀alkenyl, and a C₁ -C₁₀ alkylamino, and wherein R¹⁰ and R¹¹ may beconnected to form or be a ring; and most preferably each R¹⁰, R¹¹ andR¹² group is independently selected from the group consisting of:hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a C₅-C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₂ -C₁₀ alkenyl, a C₁ -C₁₀ alkylamino,chlorine, and bromine, and wherein any two adjacent R¹⁰, R¹¹, and R¹²groups may be joined by or be a --C₄ H₄ --, --(CH₂)₃ --, or --C₃ H₃ N--moiety;

F is represented by formula (F14): ##STR9## wherein: X³ is N or CR¹⁶ ;and

each R¹³, R¹⁴, R¹⁵, and R¹⁶ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group and wherein anytwo adjacent R¹³, R¹⁴, R¹⁵, and R¹⁶ groups may be connected to form aring, preferably each R¹³, R¹⁴, R¹⁵, and R⁶ group is independentlyselected from the group consisting of: hydrogen, halogen, a C₁ -C₂₀alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino andwherein any two adjacent R¹³, R¹⁴, R¹⁵, and R¹⁶ groups may be connectedto form a ring; more preferably each R¹³, R¹⁴, R¹⁵ and R¹⁶ group isindependently selected from the group consisting of: hydrogen, halogen,a C₁ -C₁₀ alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl,and a C₂ -C₁₀ alkenyl; and most preferably each R¹³, R¹⁴, R¹⁵, and R¹⁶group is independently selected from the group consisting of: hydrogen,methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a C₅ -C₈cycloalkyl, and phenyl;

H is represented by formula (F16): ##STR10## wherein: each R²⁰ and R²¹group is independently hydrogen, halogen, a hydrocarbyl-containinggroup, or a heterocyclic group and wherein R²⁰ and R²¹ may be connectedto form a ring, preferably each R²⁰ and R²¹ group is independentlyselected from the group consisting of: hydrogen, halogen, a C₁ -C₂₀alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino,morpholino, and furyl and wherein R²⁰ and R²¹ may be connected to formor be a saturated or unsaturated ring; more preferably each R²⁰ and R²¹group is independently selected from the group consisting of: hydrogen,halogen, a C₁ -C₁₀ alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈ cycloalkyl, a C₆-C₁₀ aryl, a C₆ -C₁₀ aryloxy, a C₂ -C₁₀ alkenyl, a C₁ -C₁₀ alkylamino, aC₆ -C₁₈ arylamino, and 2-furyl; and most preferably each R²⁰ and R²¹group is independently selected from the group consisting of: hydrogen,methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, a C₅ -C₈cycloalkyl, a C₆ -C₁₀ aryl, benzyloxy, naphthyloxy, a C₂ -C₁₀ alkenyl,diethylamino, dimethylamino, chlorine, bromine, morpholino, acetamido,and 2-furyl; and

J is represented by formula (F17): ##STR11## wherein: each R⁵, R⁶, R⁷and R⁸ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group and wherein anytwo adjacent R⁵, R⁶, R⁷ and R⁸ groups may be connected to form a ring,preferably each R⁵, R⁶, R⁷ and R⁸ group is independently selected fromthe group consisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆-C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂-C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino, morpholino, alkylamido andwherein R⁵ and R⁶ or R⁷ and R⁸ may be connected to form a ring, forexample, R⁵ and R⁶ or R⁷ and R⁸ may be joined by or be a --C₄ H₄ --,--(CH₂)₃ --, or --C₃ H₃ N-- moiety; more preferably each R⁵, R⁶, R⁷ andR⁸ group is independently selected from the group consisting of:hydrogen, halogen, a C₁ -C₁₀ alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈cycloalkyl, a C₆ -C₁₀ aryl, a C₆ -C₁₈ aryloxy, a C₂ -C₁₀ alkenyl, a C₁-C₁₀ alkylamino, a C₆ -C₁₈ arylamino, morpholino, acetamido and whereinR⁵ and R⁶ or R⁷ and R⁸ may be connected to form a 5 or 6 member ring;most preferably each R⁵, R⁶, R⁷ and R⁸ group is independently selectedfrom the group consisting of: hydrogen, methyl, ethyl, propyl, butyl,methoxy, ethoxy, propoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl,benzyloxy, naphthyloxy, a C₂ -C₁₀ alkenyl, N,N-dialkylamino,N-alkyl-N-arylamino, chlorine, bromine, morpholino, acetamido andwherein R⁵ and R⁶ or R⁷ and R⁸ may be joined by or be a --C₄ H₄ --,--(CH₂)₃ --, or --C₃ H₃ N-- moiety; and

R²³ is hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group, preferably R²³ is a group selected from the groupconsisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₃ -C₁₈ cycloalkyl, a C₆-C₁₈ aryl, a C₂ -C₁₈ alkenyl, a C₆ -C₁₈ arylamino, and substitutedsulfonyl, more preferably R²³ is selected from the group consisting ofhydrogen and --SO₂ C₆ H₅.

A particularly preferred dye is represented by the formula ##STR12##wherein each of R⁴⁸, R⁴⁹, and R⁵⁰, is independently selected from thegroup consisting of: hydrogen, halogen and an acyclic, alicyclic oraromatic hydrocarbyl group optionally interrupted with one or moreheteroatoms.

Each of R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ is independently selected fromthe group consisting of hydrogen and an acyclic, alicyclic or aromatichydrocarbyl group optionally interrupted with one or more heteroatoms.Optionally, any two of R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ may together toform an alicyclic or aromatic ring.

Preferably, at least four of R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, andR⁵⁶ are hydrogen, and more preferably at least six are hydrogen.

More preferably, each of R⁴⁸, R⁴⁹, and R⁵⁰ is independently selectedfrom the group consisting of hydrogen, alkyl and halogen; and each ofR⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ is independently selected from thegroup consisting of hydrogen and alkyl that is optionally substituted byone or more cyano, alkoxy, hydroxy, alkylsiloxy, alkylsilyl, acyl, aryl,halo, arylsiloxy, arylsilyl, amino, and mono or dialkyl amino groups.

Most preferably, at least one of R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ is

--CH₂ OSi(CH₃)₂ C(CH₃)₃

--CH₂ OC(O)CH₂ CH(CH₃)CH₂ C(CH₃)₃

--CH₂ OC(O)C(CH₃)₃

--CH₂ OCH₂ OCH₂ CH₂ Si(CH₃)₃

--CH₂ Cl

--CH₂ OC(O)NHCH₂ CH₂ CH₂ CH₃

--CH₂ OC(O)NHCH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃

Another particularly preferred dye is represented by the formula##STR13## wherein X⁴ is N--R⁶⁷ R⁶⁸, O--R⁶⁹, S--R⁷⁰ or CR⁷¹ R⁷² R⁷³ andwherein each of R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, isindependently selected from the group consisting of hydrogen, halogen, ahydrocarbyl group optionally interrupted with one or more heteroatomsand an acyclic, alicyclic or aromatic heterocyclic group, and each ofR⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰, R⁷¹, R⁷², and R⁷³ is independently selected from thegroup consisting of hydrogen, a hydrocarbyl group optionally interruptedwith one or more heteroatoms and an acyclic, alicyclic or aromaticheterocyclic group.

Preferably, at least four of R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, andR⁶⁶ are hydrogen, and more preferably at least six are hydrogen.

More preferably, each of R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰, R⁷¹, R⁷², and R⁷³ isindependently selected from the group consisting of hydrogen and alkylthat is optionally substituted by one or more cyano, alkoxy, hydroxy,alkylsiloxy, alkylsilyl, acyl, aryl, halo, arylsiloxy, arylsilyl, amino,and mono or dialkyl amino groups.

Most preferably, at least one of R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰, R⁷¹, R⁷², and R⁷³is

--CH₂ CH₂ OSi(CH₃)₂ C(CH₃)₃

--CH₂ CH₂ OC(O)CH₂ CH(CH₃)CH₂ C(CH₃)₃

--CH₂ CH₂ OC(O)C(CH₃)₃

--CH₂ CH₂ OCH₂ OCH₂ CH₂ Si(CH₃)₃

--CH₂ CH₂ Cl

--CH₂ CH₂ OC(O)NHCH₂ CH₂ CH₂ CH₃

--CH₂ CH₂ OC(O)NHCH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃

Particularly preferred compounds of this formula have the structure##STR14## Another particularly preferred dye is represented by theformula ##STR15## wherein each of R⁷⁴, R⁷⁵, R⁷⁶, R⁷⁷, R⁷⁸, R⁷⁹, R⁸⁰,R⁸¹, and R⁸⁵ is independently selected from the group consisting ofhydrogen, halogen, a hydrocarbyl group optionally interrupted with oneor more heteroatoms and an acyclic, alicyclic or aromatic heterocyclicgroup, and each of R⁸², R⁸³, and R⁸⁴ is independently selected from thegroup consisting of hydrogen, a hydrocarbyl group optionally interruptedwith one or more heteroatoms and an acyclic, alicyclic or aromaticheterocyclic group.

Preferably, at least four of R⁷⁴, R⁷⁵, R⁷⁶, R⁷⁷, R⁷⁸, R⁷⁹, R⁸⁰, R⁸¹, andR⁸⁵ are hydrogen, and more preferably at least six are hydrogen.

More preferably, each of R⁸², R⁸³, R⁸⁴ is independently selected fromthe group consisting of hydrogen and alkyl that is optionallysubstituted by one or more cyano, alkoxy, hydroxy, alkylsiloxy,alkylsilyl, acyl, aryl, halo, arylsiloxy, arylsilyl, amino, and mono ordialkyl amino.

Most preferably, at least one of R⁸², R⁸³, R⁸⁴ is

--CH₂ OSi(CH₃)₂ C(CH₃)₃

--CH₂ OC(O)CH₂ CH(CH₃)CH₂ C(CH₃)₃

--CH₂ OC(O)C(CH₃)₃

--CH₂ OCH₂ OCH₂ CH₂ Si(CH₂)₂ C(CH₃)₃

--CH₂ Cl

--CH₂ OC(O)NHCH₂ CH₂ CH₂ CH₃

--CH₂ OC(O)NHCH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃

It will be apparent to those of ordinary skill in the art that furthersubstitution of alkyl groups not involved in the conjugated electronicportion of the molecule are logical points for changing or enhancingphysical properties of the molecule, such as crystallinity, solubility,melting point, toxicology or biological activity, etc. Such substitutionmay be made without losing the essential characteristics of the moleculeas a dye, i.e., it will still exhibit color and bleaching propensitythat is the same or somewhat modified from the color and bleachingcharacteristics of the core dye structure.

Another class of particularly suitable dyes may be represented by thefollowing general formula (F18): ##STR16## wherein: each R²⁴ and R²⁵group is independently hydrogen, a hydrocarbyl-containing group, or aheterocyclic group with the proviso that at least one of R²⁴ and R²⁵ isor contains a substituted aryl, aminoaryl or heterocyclic group,preferably each R²⁴ and R²⁵ group is independently selected from thegroup consisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃-C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl,a C₂ -C₂₀ di(hydrocarbyl)amino; more preferably each R²⁴ and R²⁵ groupis a C₆ -C₁₈ aminoaryl group;

each R²⁶ and R²⁷ group is independently a --(CF₂)_(m) F group wherein mis a number between 0 and 20, more preferably m is a number between 0and 10, most preferably m is 0 or 1; and

n is an integer preferably less than 5, more preferably n is 1 or 2.

Another class of particularly suitable dyes may be represented by thefollowing general formula (F19): ##STR17## wherein: each R¹, R², R³, R⁴,and R²⁹ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group, preferably eachR¹, R², R³, R⁴ and R²⁹ group is independently selected from the groupconsisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, aC₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl,a C₂ -C₂₀ di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²), and whereinany two adjacent R¹, R², R³, R⁴ or R²⁹ group may be connected to form aring; more preferably, each R¹, R², R³, R⁴ and R²⁹ group isindependently selected from the group consisting of: hydrogen, halogen,a C₁ -C₁₀ alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl,a C₂ -C₁₀ alkenyl, and a C₁ -C₁₀ alkylamino, and wherein any twoadjacent R¹, R², R³, R⁴ or R²⁹ groups may be connected to form asaturated or unsaturated 5 to 8 member ring; most preferably each R¹,R², R⁴ and R²⁹ group is independently selected from the group consistingof: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, aC₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₂ -C₁₀ alkenyl, a C₁ -C₁₀alkylamino, chlorine, bromine;

R³⁰ is independently hydrogen, halogen, a hydrocarbyl-containing group,or a heterocyclic group, preferably R³⁰ is a group independentlyselected from the group consisting of: hydrogen, halogen, a C₁ -C₂₀alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₈ arylcarboxy, a C₆ -C₁₈carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino; morepreferably R³⁰ is a group independently selected from the groupconsisting of: hydrogen, halogen, a C₁ -C₁₀ alkyl, a C₁ -C₁₀ alkoxy, aC₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₂ -C₁₀ alkenyl, and a C₁ -C₁₀alkylamino; and most preferably R³⁰ is selected from the groupconsisting of: hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy,propoxy, a C₅ -C₈ cycloalkyl, and a C₆ -C₁₀ aryl;

n is an integer preferably less than 5, more preferably n is 1 or 2.

Another class of particularly suitable dyes includes anionic oxonol dyeshaving the following general formula (F20): ##STR18## wherein: Zrepresents the non-metallic atoms necessary to complete a substituted orunsubstituted nitrogen-containing heterocyclic ring, preferably thenon-metallic atoms are selected from the group consisting of O, N, C andS,

each R²⁸ is independently hydrogen, a hydrocarbyl-containing group, or aheterocyclic group, preferably each R²⁸ is independently selected fromthe group consisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈carboxyaryl, a C₂ -C₁₈ alkenyl, a C₆ -C₁₈ aminoaryl; more preferablyeach R²⁸ is independently selected from the group consisting of:hydrogen, a C₁ -C₁₀ alkyl, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, and a C₂-C₁₀ alkenyl;

n is an integer preferably less than 5, more preferably 1 or 2; andwherein

M+ is selected from any suitable cation including sodium,triethylammonium and the like.

Another class of particularly suitable dyes includes cationic dyeshaving the following general formula (F30): ##STR19## wherein: each R³¹,R³², R³³, and R³⁴ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group; preferably eachR³¹, R³², R³³, and R³⁴ group is independently selected from the groupconsisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, aC₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl,a C₂ -C₂₀ di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²), and whereinany two adjacent R³¹, R³², R³³, or R³⁴ groups may be connected to form aring; more preferably each R³¹, R³², R³³, and R³⁴ group is independentlyselected from the group consisting of: hydrogen, halogen, a C₁ -C₁₀alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₂ -C₁₀alkenyl, and a C₁ -C₁₀ alkylamino, and wherein any two adjacent R³¹,R³², R³³, or R³⁴ groups may be connected to form a 5 to 8 member ring;and most preferably each R³¹, R³², R³³, and R³⁴ group is independentlyselected from the group consisting of: hydrogen, methyl, ethyl, propyl,butyl, methoxy, ethoxy, propoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, aC₂ -C₁₀ alkenyl, a C₁ -C₁₀ alkylamino, chlorine, bromine, and whereinR³³ and R³⁴ may be joined by a --C₄ H₄ --, --(CH₂)₃ --, or --C₃ H₃ N--moiety;

R³⁵ and R³⁶ are as defined above for R³³ and R³⁴ ;

X is O, S, or NR³⁷ ;

Y is N or CR³⁸ ;

R³⁷ and R³⁸ are as defined above for R³³ ; and wherein

M- is any suitable anion.

Another class of particularly suitable dyes includes cationic dyeshaving the following general formula (F31): ##STR20## wherein: each R³¹,R³², R³³, and R³⁴ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group, preferably eachR³¹, R³², R³³, and R³⁴ group is independently selected from the groupconsisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, aC₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl,a C₂ -C₂₀ di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²), and whereinany two adjacent R³¹, R³², R³³, or R³⁴ groups may be connected to form aring; more preferably each R³¹, R³², R³³, and R³⁴ group is independentlyselected from the group consisting of: hydrogen, halogen, a C₁ -C₁₀alkyl, a C₁ -C₁₀ alkoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, a C₂ -C₁₀alkenyl, and a C₁ -C₁₀ alkylamino, and wherein any two adjacent R³¹,R³², R³³, or R³⁴ groups may be connected to form a 5 to 8 member ring;and most preferably each R³¹, R³², R³³, and R³⁴ group is independentlyselected from the group consisting of: hydrogen, methyl, ethyl, propyl,butyl, methoxy, ethoxy, propoxy, a C₅ -C₈ cycloalkyl, a C₆ -C₁₀ aryl, aC₂ -C₁₀ alkenyl, a C₁ -C₁₀ alkylamino, chlorine, bromine, and whereinR³³ and R³⁴ may be joined by a --C₄ H₄ --, --(CH₂)₃ --, or --C₃ H₃ N--moiety;

R³⁹ is independently hydrogen, a hydrocarbyl-containing group or aheterocyclic group, preferably R³⁹ is a group selected from the groupconsisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₃ -C₁₈ cycloalkyl, a C₆-C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C_(1-C) ₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino;

R⁴⁰ is independently hydrogen, halogen, a hydrocarbyl-containing group,or a heterocyclic group, preferably R⁴⁰ is a group selected from thegroup consisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆-C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂-C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino, and carboxamide;

X is C═R⁴⁸, C(R³⁸)₂, O, S, or NR³⁷, more preferably X is C═R⁴⁸, C(R³⁸)₂or S, wherein

R³⁷ is as defined above for R³⁹,

R³⁸ is as defined above for R⁴⁰,

R⁴⁸ is an oxo group, a divalent hydrocarbyl-containing group, or adivalent heterocyclic group, wherein R⁴⁸ and R³⁴ may be connected toform an unsaturated ring, for example, R⁴⁸ and R³⁴ may be joined by a--C₃ H₃ -- moiety, and wherein R³⁷ and R³⁴ may be connected to form asaturated or unsaturated ring; and wherein

M- is any suitable anion.

Another class of particularly suitable dyes includes cationic dyeshaving the following general formula (F32): ##STR21## wherein: each R⁴²to R⁴⁵ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group, preferably eachR⁴² to R⁴⁵ group is independently selected from the group consisting of:hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, aC₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino,

each R⁴⁰, R⁴¹, R⁴⁶ and R⁴⁷ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group, preferably eachR⁴⁰, R⁴¹, R⁴⁶ and R⁴⁷ group is independently selected from the groupconsisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₃ -C₁₈ cycloalkyl, a C₆-C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, wherein any two adjacent R⁴¹ to R⁴³ groups may beconnected to form a ring and wherein R⁴⁴ and R⁴⁵ may be connected toform a ring; more preferably R⁴⁰, R⁴¹, R⁴⁶ and R⁴⁷ are methyl and R⁴² toR⁴⁵ are hydrogen;

n is an integer preferably less than 5, more preferably 1, 2 or 3; andwherein

M- is any suitable anion.

Suitable cure-indicator dyes for use in the present invention includeneutral dyes such as:4-[[4-(Dimethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;4-[[4-(Diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[4-(Dimethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[2-methyl-4-(diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;3-Methoxy-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Methyl-4-[[4-(4-morpholinyl)phenyl]-imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[4-(4-morpholinyl)-phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dimethyl-4-[[4-(4-morpholinyl)-phenyl]imino]-2,5-cyclohexadien-1-one;2,5-Dichloro-4-[[4-(diethylamino)-phenyl]imino]-2,5-cyclohexadien-1-one;3-Methoxy-4-[[3-methoxy-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-[[4-(Diethylamino)-2-methylphenyl]imino]-6-oxo-N-phenyl-1,4-cyclohexadiene-1-carboxamide;5-[[4-(Diethylamino)-2-methylphenyl]imino]-8-(5H)-quinolinone;2,5-Dichloro-4-[[2-methyl-4-(diethylamino)-phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[4-(acetamido)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4-ethoxy phenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(2-methyl-4-ethoxyphenyl)imino]-2,5-cyclohexadien-1-one; 2,6-Dimethyl-4-[4-hydroxyphenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(4-methoxy-1-naphthyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[4-(benzyloxy)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(2,4-dimethoxyphenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(4-methoxyphenyl)imino]-2,5-cyclohexadien-1-one;4-(phenylimino)-2,5-cyclohexadien-1-one;4-(1-naphthylimino)-2,5-cyclohexadien-1-one;4-(2-napthylimino)-2,5-cyclohexadien-1-one;2,5-Bis(phenylamino)-4(phenylimino)-2,5-cyclohexadien-1-one;2,5-Dibromo-4-[(2,4-dibromophenyl)imino]-2,5-cyclohexadien-1-one;2,3,5-Trichloro-4-[(2,4,6-trichlorophenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4-[4-(dimethylamino)phenyl]-5-phenyl-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4,5-bis(4-hydroxyphenyl)-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Dimethoxy-4-[4,5-bis(2-furyl)-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Bis[1,1-(dimethyl)ethyl]-4-[4,5-bis(2-furyl)-(2H)-imidazol-2-ylidene]-2,5-cyclohexadiene-1-one;4-(phenylimino)-2,5-cyclohexadien-1-imine;Mono[(3-methyl-2-(3H)-benzothiazolylidene)hydrazono]2,5-cyclohexadiene-1,4-dione;4-[(3-Chloro-4-oxo-2,5-cyclohexadien-1-ylidine)amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-(3H)-pyrazol-3-one;4-[(3,5-Dichloro-4-oxo-2,5-cyclohexadien-1-ylidine)amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-(3H)-pyrazol-3-one;3-[(3,5-Dichloro-4-oxo-2,5-cyclohexadien-1-ylidine)amino]-2,5-dihydro-4,5-dimethyl-1-phenylpyrrol-2-one;4-(Phenylsulfonyl)imino-1-[4-[(phenylsulfonyl)imino]-2,5-cyclohexadien-1-ylidenyl]-2,5-cyclohexadiene;4-[6,6-Bis[(trifluoromethyl)sulfonyl]-1,3,5-hexatrienyl]-N,N-dimethylbenzenamine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2-ethoxy-N,N-dimethylbenzenamine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,5-dimethoxy-N,N-dimethylbenzenamine;9-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,3,6,7-tetrahydro-(1H,5H)-benzo[ij]quinolizine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,6-N,N-tetramethyl-benzenamine;4-[5,5-Bis[(trifluoromethyl)sulfonyl]-2,4-pentadienylidene]-1,4-dihydro-1-methylquinoline;6,6-Bis[4-(dimethylamino)phenyl]1,3,5-hexatriene-1,1-bis(sulfonylfluoride);4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-N,N-dimethylbenzenamine;and4-[3-[4-(Dimethylamino)phenyl]-2-propenylidene]-2-phenyl-5(4H)-oxazolone;anionic dyes having the following anions:5-[5-(1,3-Diethylhexahydro-2,4,6-trioxo-5-pyrimidinyl)-2,4-pentadienylidene]-1,3-diethyl-2,4,6(1H,3H,5H)-pyrimidenetrione;and cationic dyes having the following cations or having the cations ofthe following cationic dyes: 3H-Indolium,3-[3-[4-(dimethylamino)phenyl]-2-propenylidene]-1-methyl-2-phenyl;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-[bis(2-chloroethyl)amino]phenyl]azo]-6-methoxy-;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-(diethylamino)phenyl]azo]-6-ethoxy-;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-(diethylamino)-2-methylphenyl]azo]-6-ethoxy-;CAS 12221-40-8; CAS 12270-14-3; CAS 12221-31-7; CAS 12221-34-0;Benzo[a]phenoxazin-7-ium, 9-(dimethylamino)-;2-[4,4,-bis[4-dimethylamino)phenyl]-1,3-butadienyl]-1-ethyl quinolinium;4-[4,4,-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]1-ethyl quinolinium;Naphtho[2,1-d]thiazolium,2-[4,4-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]-3-ethyl-;2-[2-[4-(dimethylamino)phenyl]ethenyl]-1-phenyl-3-methyl quinoxalinium;Quinolinium,2-[3-(5-chloro-1,3-dihydro-1,3,3-trimethyl-(2H)-indol-2-ylidene)-1-propenyl]-1-methyl-;Benzothiazolium, 2-[[4-(dimethylamino)phenyl]azo]-6-methoxy-3-methyl-;Benz[cd]indolium, 2-[4-(diethylamino)-2-ethoxyphenyl]-1-ethyl-;2-[p-(Dimethylamino)styryl]-1,3-dimethylquinoxalinium;2-[3-(5-chloro-1,3-dihydro-1,3,3-trimethyl-(2H)-indol-2-ylidene)-1-propenyl]-1-methylquinoxalinium;C. I. Basic Blue 40; Benzothiazolium,2-[[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-6-methoxy-3-methyl-;Benzothiazolium,2-[[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-6-methoxy-3-methyl-; C. I.Basic Blue 42; C. I. Basic Blue 53; 3H-Indolium,5-chloro-2-[5-(5-chloro-1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-1,3-pentadienyl]-1,3,3-trimethyl-;Basic Blue 142; Benz[cd]indolium,2-[2-(9-ethyl-(9H)-carbazol-3-yl)ethenyl]-1-methyl-; Benz[cd]indolium,2-[2-[4-(dimethylamino)phenyl]-2-phenylethenyl]-1-methyl-;Benz[cd]indolium, 2-[2,2-bis[4-(dimethylamino)phenyl]ethenyl]-1-methyl-;Benz[cd]indolium,2-[2-(2,3-dihydro-1-methyl-2-phenyl-1H-indol-3-yl)-2-(2-methylphenyl)ethenyl]-1-methyl-;Pyrimidinium, 4-[5-(2,3-dihydro-1,3-dimethyl-2-oxo-;4(1H)-pyrimidinylidene)-1,3-pentadienyl]-2,3-dihydro-1,3-dimethyl-2-oxo-;3H-Indolium,2-[[3-[(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)methyl]-5,5-dimethyl-2-cyclohexen-1-ylidene]methyl]-1,3,3-trimethyl-;Benz[cd]indolium,2-[2-[4-(diethylamino)-2-methylphenyl]ethenyl]-1-methyl-; 3H-Indolium,3-[3-[4-[(dimethylamino)phenyl]-2-propenylidene]-1-methyl-2-(4-methoxyphenyl)-;3H-Indolium,3-[(2,5-dimethyl-1-phenyl-(1H)-pyrrol-3-yl)methylene]-1,2-dimethyl-;3H-Indolium,3-[2,5-dimethyl-1-phenyl-(1H)-pyrrol-3-yl)methylene]-1-methyl-2-phenyl-;2-[2-[2-chloro-4-(dimethylamino)phenyl]ethenyl]-1-methylbenz[cd]indolium;C. I. Basic Violet 22; C. I. Basic Red 15; Benz[cd]indolium,2-[2-[4-(dimethylamino)phenyl]ethenyl]-1-methyl-;Benz[cd]indolium,2-[2-[4-(dimethylamino)-2-ethoxyphenyl]ethenyl]-1-methyl-;and 3H-Indolium,2-[1-cyano-4,4-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]-1,3,3-trimethyl-.

Presently particularly preferred dyes for use in the present inventioninclude: 4-[[4-(Dimethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;4-[[4-(Diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[4-(Dimethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[2-methyl-4-(diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;3-Methoxy-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Methyl-4-[[4-(4-morpholinyl)phenyl]imino]-2,5-cyclohexadien-1-one;2,5-Dichloro-4-[[4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-[[4-(Diethylamino)-2-methylphenyl]imino]-6-oxo-N-phenyl-1,4-cyclohexadiene-1-carboxamide;5-[[4-(diethylamino)-2-methylphenyl]imino]-8-(5H)-quinolinone;2,6-Dichloro-4-[[4-(acetamido)phenyl]imino]-2,5-cyclohexadien-1-one;4-(1-naphthylimino)-2,5-cyclohexadien-1-one;4-(2-naphthylimino)-2,5-cyclohexadien-1-one;2,5-Bis(phenylamino)-4(phenylimino)-2,5-cyclohexadien-1-one;4-[5,5-Bis[(trifluoromethyl)sulfonyl]-2,4-pentadienylidene]-1,4-dihydro-1-methylquinoline;6,6-Bis[4-(dimethylamino)phenyl]1,3,5-hexatriene-1,1-bis(sulfonylfluoride);4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-N,N-dimethylbenzenamine;and4-[3-[4-(Dimethylamino)phenyl]-2-propenylidene]-2-phenyl-5(4H)-oxazolone.

A variety of adjuvants may be utilized to modify the relationshipbetween the color change and the extent of cure. These adjuvants aregenerally added to the primary compositions of this invention in anamount suitable to obtain the desired interactions. Several suitableclasses of indicator adjuvants include active proton sources such asalcohols, acids, and water. Alternatively, a variety of hydrosilationinhibitors well known in the art may also serve as adjuvants such asacetylenic alcohols, certain polyolefinic siloxanes, pyridine,acrylonitrile, organic phosphines and phosphites, unsaturated amides,alkyl fumarates, alkyl maleates and the like.

As previously mentioned the composition containing the cure-indicatingdye optionally may comprise one or more suitable solubilizing agents(e.g., surfactants). The surfactants may be employed to facilitate ormaintain the dissolution or dispersion of the cure-indicating dye and/orother ingredients in the composition, to facilitate uniform mixing ofthe reactants, or to adjust the composition's viscosity or flow. Thesurfactant may also be employed to modify the surface wettingcharacteristics of the composition. In particular, the surfactant may bedesired when the composition comprises a filler. Suitable surfactantsfor use with silicone compositions include surfactants selected from thegroup consisting of ethoxylated nonionic surface active agents andcationic or amphoteric fluorochemical surface active agents such asthose disclosed in U.S. Pat. No. 4,657,959 (Bryan et al.) which isherein incorporated by reference. Preferred surfactants contain one ormore solubilizing groups (e.g., one or more siloxane groups,hydrocarbyl-containing groups or perfluoroalkyl groups) which render thesurfactant soluble or dispersible in the silicone composition.

A preferred class of ethoxylated surfactants containing a siloxanesolubilizing group has the average formula ##STR22## where each R isindependently a monovalent hydrocarbyl radical, R¹ is a divalenthydrocarbylene radical, each R² is independently hydrogen or a lowerhydroxyalkyl radical, R³ is hydrogen or a monovalent hydrocarbylradical; x, a, and b are independently greater than or equal to zero;and y is independently greater than or equal to one. Preferably incompounds of Formula I, R is methyl, R¹ is methylene (--CH₂ --),ethylene (--CH₂ CH₂ --), propylene (CH₂ CH₂ CH₂ --) or butylene (--CH₂CH₂ CH₂ CH₂ --), R² is hydrogen, R³ is hydrogen, methyl, ethyl, propyl,or butyl, x is a number from zero to 100, y is a number from one tofive, a is a number from 5 to 300, and b is a number from zero to 300;more preferably R is methyl, R¹ is ethylene or propylene, R² ishydrogen, R³ is hydrogen, methyl, or butyl, x is a number from zero to80, y is a number from one to five, a is a number from 5 to 200, and bis a number from zero to 200; most preferably R is methyl, R¹ ispropylene, R² is hydrogen, R³ is hydrogen, methyl, or butyl, x is anumber from zero to 60, y is a number from one to five, a is a numbersuch that the product of y times a is zero to 200, and b is a numbersuch that the product of y times b is zero to 200, and the sum of theproduct of a times y and b times y is five to 200.

Another preferred class of ethoxylated surfactants has the averageformula

    RSi.brket open-st.(OSi).sub.x (OC.sub.2 H.sub.3 R.sup.2).sub.a (OC.sub.3 H.sub.6).sub.b OR.sup.3 ].sub.3                           II

where R, R², R³, x, a and b are as defined above for formula I.Preferably in compounds of Formula II, R and R³ are --CH₃, R² ishydrogen, a is five to 20 and b is zero.

Ethoxylated surfactants of Formulas I and II above are described inUnion Carbide Corp. product literature ("Silwet Surfactants," datedAugust, 1992; "Organomodified Oils [OMO]," dated April, 1982; "UCAR-SILEPS Silicone Hydrophilic Finish," dated March 1984 and available fromOSi Specialties, Inc., Danbury, Conn.) and in U.S. Pat. Nos. 3,505,377,3,980,688, and 4,431,789, the disclosures of which are incorporatedherein by reference. Several of such ethoxylated surfactants areavailable from OSi Specialties, Inc. as "SILWET" surface activecopolymers. Preferred SILWET surface active copolymers include SILWETL-77, L-7607, L-7630, L-7002 and L-7200.

An additional preferred class of ethoxylated surfactants has the averageformula ##STR23## where R² and R³ are as defined above for Formula I,each R⁴ group is independently a monovalent hydrocarbyl radical with theproviso that at least a majority of the R⁴ groups are stericallyhindered alkyl radicals having at least three carbon atoms, c is atleast four, d is greater than or equal to zero, and T is hydrogen, amonovalent alkyl or alkenyl radical, or a group of the formula--Si(R³)₂[OSi(OR⁴)₃ ]₂. Preferably in compounds of Formula III, R² is hydrogen,R³ and T are --CH₃, R⁴ is sec-butyl, c is five or more and d is zero.Representative ethoxylated surfactants of Formula III are described inOlin Corp. product literature ("Silicate ClusterO Fluids") and in U.S.Pat. Nos. 4,160,776, 4,226,794, and 4,337,168, the disclosures of whichare incorporated herein by reference. At least one such surfactant isexperimentally available from Olin Corp. as a "SILFAC" polyethoxylatedsilicate cluster compound bearing the experimental designation "SILFAC12M".

An additional preferred class of ethoxylated surfactants has the averageformula

    (R.sup.4 O).sub.3 Si(OC.sub.2 H.sub.3 R.sup.2).sub.e (OC.sub.3 H.sub.6).sub.f OT.sup.1                                   IV

where R² and R⁴ are as defined above for Formula III, e is at leastfour, f is greater than or equal to zero, and T¹ is hydrogen, amonovalent alkyl or alkenyl radical, or a group of the formula--Si(OR⁴)₃. The preparation of these ethoxylated surfactants isdescribed in U.S. Pat. No. 4,657,959. Preferably in compounds of FormulaIV, R² is hydrogen, R⁴ is sec-butyl, e is ten to 20, f is zero and T¹ is--Si(secbutoxy)₃.

Suitable ethoxylated surfactants containing hydrocarbyl solubilizinggroups are shown in "Surfactants and Detersive Systems", Kirk-OthmerEncyclopedia of Chemical Technology, 3rd Ed., 22, 360-377 (1983), thedisclosure of which is incorporated herein by reference. A preferredclass of such ethoxylated surfactants has the average formula

    R.sup.5 [(OC.sub.2 H.sub.3 R.sup.2).sub.g (OC.sub.3 H.sub.6).sub.1 OR.sup.3 ].sub.1 to 3                                              V

where R² and R³ are as defined above for Formula I, R⁵ is a saturated orunsaturated alkyl or alkylphenyl radical having at least seven carbonatoms, g is a number from zero to 100, 1 is a number from zero to 100,and the sum of g and 1 is at least three.

Suitable ethoxylated surfactants containing perfluoroalkyl solubilizinggroups are described in U.S. Pat. No. 2,915,544, the disclosure of whichis incorporated herein by reference. A preferred class of suchethoxylated surfactants has the average formula

    Rf--[Q(C.sub.2 H.sub.3 R.sup.2 O).sub.h (C.sub.3 H.sub.6 O).sub.i R.sup.3 ].sub.1 or 2                                              VI

where R² and R³ are as defined above for Formula I, Rf is a fluorinated,monovalent or divalent, aliphatic, preferably saturated organic radicalcontaining at least four carbon atoms and preferably a terminalperfluoromethyl group, Q is a polyvalent (e.g., divalent) hydrocarbylenelinking group (e.g., --C₂ H₄ --, or --SO₂ NR-- where R is as definedabove), h is greater than or equal to one, and i is greater than orequal to zero.

The surfactant used in the present invention can also be a cationic oramphoteric fluorosurfactant. Such fluorosurfactants contain at least oneperfluoroalkyl solubilizing group Rf where Rf is as defined above forFormula VI. The cationic fluorosurfactants contain at least onecationogenic group which is the radical of a base having an ionizationconstant in water at 25° C. of at least about 10⁻⁶. The amphotericfluorosurfactants contain at least one such cationogenic group and atleast one anionogenic group which is the radical of an acid having anionization constant in water at 25° C. of at least about 10⁻⁶. Suitablefluorosurfactants are described, for example, in U.S. Pat. No.4,484,990, the disclosure of which is incorporated herein by reference.

Other suitable solubilizing or wetting agents include substances such aspoly(ethylene oxide), poly(propylene oxide), and copolymers of ethyleneoxide and propylene oxide. Suitable such substances have the averageformula

    R.sup.1 O(C.sub.2 H.sub.3 R.sup.2 O).sub.j (C.sub.3 H.sub.6 O).sub.k R.sup.3VII

where

R² is as defined above for Formula I,

each R¹ and R³ group is independently hydrogen, a hydrocarbyl-containinggroup, or a heterocyclic group, preferably R² is hydrogen and each R¹and R³ is selected from the group consisting of hydrogen, a C₁ -C₂₀alkyl, and a C₁ -C₂₀ alkylphenyl group, more preferably each R¹ and R²is hydrogen;

j is a number having an average value between 0 and 25, more preferablyj is a number having an average value between 5 and 15;

k is a number having an average value between 0 and 100, more preferablyk is a number having an average value of 0; and wherein

the sum of j and k is at least 3.

Preferred wetting agents of this class include hydroxy terminatedpoly(ethylene oxide), hydroxy terminated poly(propylene oxide), andhydroxy terminated copolymers of ethylene oxide and propylene oxide(also known as polyethylene glycols, polypropylene glycols, andcopolymers thereof).

The following examples are offered to aid in the understanding of thepresent invention and are not to be construed as limiting the scopethereof. Unless otherwise indicated, all parts and percentages are byweight

EXAMPLES Preparatory Example 1a Preparation of a Karstedt catalyst

A three neck flask was fitted with a mechanical stirrer, refluxcondenser, thermometer, and nitrogen purge and placed in a water bath.The flask was charged with 3,000 parts ethanol and 1,200 parts1,1,3,3-tetramethyl-1,3-divinyldisiloxane and then purged with nitrogenfor 5 minutes. Six hundred parts hexachloroplatinic acid was added tothe solution and the mixture stirred until the acid was substantiallydissolved. Eighteen hundred parts sodium bicarbonate was then added overa 5 minute period. The water bath was heated to 60° C. and then stirredfor 2.5 hours. After it had cooled, the solution was filtered, washedwith 150 parts ethanol and transferred to a flask containing 6,000 partsdimethylvinylsiloxy terminated polydimethylsiloxane with a viscosity of0.3 Pa s and a molecular weight of about 10,000 g/mol. The flask wasplaced on a rotary evaporator and stripped at 45° C. until the vacuumreaches 0.5-1.0 Torr to produce a Karstedt type catalyst solution with aplatinum concentration of approximately 2.3-3.0%.

Preparatory Example 1b Preparation of a Catalyst Complex of Pt^(o) andDivinyltetramethyldisiloxane

Preparation of: Bis(1,5-cyclooctadiene)platinum(0):

To a suspension of lithium ribbon (0.7 g, 100 mmol) in diethyl ether (80ml) at 0° C. under argon was added freshly distilled1,3,5,7-cyclooctatetraene, ("COT"), (2.5 g, 24 mmol), and the resultantmixture was allowed to come slowly to room temperature and was stirredovernight. A 2.0 ml aliquot of the dark orange solution was hydrolyzedin approximately 2 ml of water, approximately 1 mg of phenolphthaleinwas added, and titration with 1.00N HCl required 1.05 ml to reach theendpoint, indicating a 0.25M solution of (COT)Li₂. A substantial amountof white solids settled from the solution.

A 250-ml three-necked round-bottomed flask equipped with a magnetic stirbar and fitted with a 60-ml addition funnel was flushed with argon andcharged with 3.7 g, 10 mmol finely ground (COD)PtCl₂ (as described byMcDermott, White, and Whitesides, in J. Am. Chem. Soc. 1976, 98, 6521)and 1,5-cyclooctadiene, ("COD"), (15 ml). The mixture was cooled tominus 40° C., and the addition funnel was charged with the 0.25Msolution of (COT)Li₂ in diethyl ether, prepared above, (41 ml, 10 mmol),which was added dropwise to the rapidly stirred slurry over a period of45 min. After the addition was complete, the orange mixture was allowedto warm to 0° C. over the course of 1 hour. Volatile materials wereseparated at reduced pressure until the residue was quite dry. Argon wasreadmitted to the flask, and the orange residue was extracted at roomtemperature with five 50 ml portions of toluene. The combined extractswere filtered through a short column of alumina (8×2.5 cm, neutralBrockman activity II). The column was washed with an additional 50-mlportion of toluene, and the volume of the filtrate and washings wasreduced by approximately one-half under reduced pressure. Thereddish-brown solution was cooled to minus 20° C. and allowed to standfor approximately 60 hours during which time white crystals formed. Themother liquor was separated, and the crystals were washed with four 5 mlportions of diethyl ether and dried under vacuum to yield a first cropof 1.09 g product. The mother liquor was concentrated to dryness underreduced pressure, and the brown residue was washed with five 5 mlportions of diethyl ether and dried under vacuum to give a second cropof 0.58 g. The ¹ H NMR spectra of the first and second crop wereidentical, consistent for the desired complex and in agreement withpublished data by Spencer (Spencer, J. L. Inorg. Synth. 1979, 19, 213).Preparation of:Tris(1,3-divinyl-1,1,3,3-tetramethyldisiloxane)diplatinum(0):

Bis(1,5-cyclooctadiene)platinum(0) (600 mg, 1.46 mmol) was added insmall portions to a rapidly stirred solution of1,3-divinyl-1,1,3,3-tetramethyldisiloxane (405 mg, 2.17 mmol) in diethylether (15 ml) at room temperature under argon. The mixture was stirredovernight, and concentration under reduced pressure afforded a colorlessoil. The crude product was purified by first eluting from Florisil withdiethyl ether followed, after concentration, by flash chromatography onsilica gel with 98:2 hexanes--diethyl ether. The product was obtained asa colorless oil, homogeneous by TLC, which crystallized on standing. ¹H, ¹³ C, ²⁹ Si, and ¹⁹⁵ Pt NMR analyses were consistent for the desiredcomplex and in agreement with published data by Hitchcock et al.(Hitchcock, P. B.; Lappert, M. F.; Warhurst, N. J. W. Angew. Chem., Int.Ed. Engl. 1991, 30, 438).

The above complex (with the theoretical structure of F25) was dissolvedin toluene to provide a catalyst solution having between about 2 and 3weight percent platinum. ##STR24##

Preparatory Example 2

Stock "catalyst" compositions and stock "base" compositions wereprepared by combining the following ingredients as listed in Table P2:

                  TABLE P2                                                        ______________________________________                                                         Stock Composition                                            Ingredient    Structure                                                                              B1     C1   B2    C2                                   ______________________________________                                        Vinyl terminated                                                                            F21      78.35  97.95                                                                              78.35 97.95                                polydimethylsiloxane.sup.1                                                    Crosslinker.sup.2                                                                           F22      21.97  --   21.97 --                                   Inhibitor.sup.3                                                                             F23       0.06  --    0.06 --                                   Catalyst.sup.4                                                                              F24      --      2.05                                                                              --     2.05                                Dichloromethane        --     --   100.3 100.0                                ______________________________________                                         .sup.1 "Vinyl terminated polydimethylsiloxane" =                              (vinyldimethylsiloxy)terminated polydimethylsiloxane with a viscosity of      approximately 2 Pa s ("LMWP") and available as Y7942 from OSi Specialties     Inc., Danbury, CT.                                                            ##STR25##                                                                     .sup.2 "Crosslinker" = organohydropolysiloxane having a viscosity of          approximately 24 to 38 mPa s and approximately 0.2% hydride ("XL1") and       available from OSi Specialties, Inc., Danbury, CT.                            ##STR26##                                                                     .sup.3 "Inhibitor" = 1,3divinyltetramethyldisiloxane ("DVTMDS") and           available from United Chemical Technology, Inc., Bristol, PA.                 ##STR27##                                                                     .sup.4 "Catalyst" = Karstedt type platinum catalyst comprising 2.55 wt %      platinum catalyst in vinyl terminated polydimethylsiloxane (as described      in Preparatory Example 1a and as shown with the approximate formula of        structure F24).                                                               ##STR28##                                                                

Preparatory Example 3 Preparation of Various Dyes

Preparation of:2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one:

1450 parts K₃ Fe(CN)₆, 595 parts Na₂ CO₃, and 4150 parts water wereadded to a 12-liter round bottom flask equipped with a mechanicalstirrer, thermometer, and addition funnel. The mixture was heated to 55°C. with stirring. A solution of 227 parts4-(N,N-diethylamino)-2-methylaniline monohydrochloride, 128 partso-chlorophenol, 1960 parts ethanol, and 2500 parts water was charged tothe addition funnel and added dropwise to the stirred, heated solution.After the addition was complete the reaction mixture was maintained at55° C. with stirring for 20 minutes. The warm mixture was filtered withvacuum and the resulting filter cake was placed in a solution of 296parts ethanol and 1125 parts water to form a slurry. The dye wasisolated by vacuum filtration. This process was repeated two times,first with 296 parts ethanol and 1125 parts water, then with 608 partsmethanol. After the final vacuum filtration the filter cake was dried at40° C. under vacuum for 48 hours. Yield was ˜90%. The final product canbe recrystallized from ethyl acetate or ethanol.

The preparation of other indoaniline dyes is described by MasafumiAdachi et al. in the Journal of Organic Chemistry (J. Org. Chem. 1993,58, 5238-5244) which is herein incorporated by reference. This paperdescribes a procedure of preparing dyes by oxidative condensation ofsuitable p-phenylenediamines and phenols using ammonium persulfate asthe oxidant (following the procedure outlined in by Vittum et al. in theJ. Am. Chem. Soc. 1946, 68, 2235).

The preparation of various sulfone dyes is described in U.S. Pat. Nos.3,933,914, 4,018,810, and 4,357,405; U.S. patent application Ser. No.07/730,225 now U.S. Pat. No. 5,360,582; and in Zhurnal OrganicheskoiKhimii, Vol. 15, No. 11, pages 2416 and 2417 (November 1979), which areherein incorporated by reference.

Example 1

A variety of dyes were evaluated as cure indicators by the followingprocedure. Approximately 0.0005 grams (500 μg) of a dye, as listed inTable 1a, was transferred to a 1.5 dram (6 ml) clear glass vialcontaining two drops (˜200 mg) of dichloromethane. Approximately 1 ml ofstock composition B2 was transferred to the vial and the solution mixedwith a spatula until homogeneous. Approximately 1 ml of stockcomposition C2 was transferred to the colored solution, a timer startedand the composition was mixed thoroughly for 30 seconds. The compositionwas placed against a white background and visually examined for the timeat which "gelation" and visual color change occurred. Gel times ("GT")were recorded and it was determined if a color change occurred beforethe gel point, within two times the gel point and/or following 24 hrs atroom temperature. Set out in Table 1b are the results observed for thesedyes.

                  TABLE 1a                                                        ______________________________________                                                                     Further                                                                       Identification                                   Dye                          and/or                                           #    Identification.sup.1,4  Comments                                         ______________________________________                                        1    4-[[4-(Dimethylamino)phenyl]imino]-2,5-                                                               Phenol Blue                                           cyclohexadien-1-one                                                      2    2-Chloro-4-[[2-methyl-4-(diethylamino)-                                                               CAS 68155-95-3                                        phenyl]imino]-2,5-cyclohexadien-1-one                                    3    4-[[4-(Diethylamino)phenyl]imino]-                                                                    Colour Index                                          1,4-dihydronaphthalen-1-one                                                                           49705;                                                                        C.I. Solvent                                                                  Blue 22                                          4    4-[[4-(Dimethylamino)phenyl]imino]-                                                                   Colour Index                                          1,4-dihydronaphthalen-1-one                                                                           49700                                            5    4-[[2-methyl-4-(diethylamino)-                                                phenyl]imino]-1,4-dihydronaphthalen-1-one                                6    3-Methoxy-4-[[2-methyl-4-(diethylamino)-                                      phenyl]imino]-2,5-cyclohexadien-1-one                                    7    3-Chloro-4-[[2-methyl-4-(diethylamino)-                                       phenyl]imino]-2,5-cyclohexadien-1-one                                    8    2-Methyl-4-[[4-(4-morpholinyl)-                                               phenyl]imino]-2,5-cyclohexadien-1-one                                    9    same as #8                                                               10   2,6-Dichloro-4-[[4-(4-morpholinyl)-                                           phenyl]imino]-2,5-cyclohexadien-1-one                                    11   2,6-Dimethyl-4-[[4-(4-morpholinyl)-                                           phenyl]imino]-2,5-cyclohexadien-1-one                                    12   2,5-Dichloro-4-[[4-(diethylamino)-                                            phenyl]imino]-2,5-cyclohexadien-1-one                                    13   3-Methoxy-4-[[3-methoxy-4-(diethyl-                                           amino)phenyl]imino]-2,5-cyclohexadien-                                        1-one                                                                    14   2,6-Dichloro-4-[[2-methyl-4-(diethyl-                                         amino)phenyl]imino]-2,5-cyclohexadien-                                        1-one                                                                    15   3-[[4-(Diethylamino)-2-methyl-                                                                        CAS                                                   phenyl]imino]-6-oxo-N-phenyl-                                                                         102187-32-6                                           1,4-cyclohexadiene-1-carboxamide                                         16   5-[[4-(Diethylamino)-2-methyl-                                                                        CAS 54033-12-4                                        phenyl]imino]-8-(5H)-quinolinone                                         17   2,5-Dichloro-4-[[2-methyl-4-(diethyl-                                         amino)phenyl]imino]-2,5-cyclohexadiene-                                       1-one                                                                    18   2,6-Dichloro-4-[4-ethoxyphenyl)imino]-                                        2,5-cyclohexadien-1-one                                                  19   2,6-Dichloro-4-[(2-methyl-4-ethoxy                                            phenyl)imino]-2,5-cyclohexadien-1-one                                    20   2,6-Dimethyl-4-[4-hydroxy phenyl)imino]-                                      2,5-cyclohexadien-1-one                                                  21   2,6-Dichloro-4-[(4-methoxy-1-naphthyl)-                                       imino]-2,5-cyclohexadien-1-one                                           22   2,6-Dichloro-4-[[4-(benzyloxy)-                                               phenyl]imino]-2,5-cyclohexadien-1-one                                    23   2,6-Dichloro-4-[(2,4-dimethoxyphenyl)-                                        imino]-2,5-cyclohexadien-1-one                                           24   same as #18                                                              25   same as #21                                                              26   2,6-Dichloro-4-[(4-methoxyphenyl)imino]-                                      2,5-cyclohexadien-1-one                                                  27   same as #23                                                              28   same as #23                                                              29   4-(phenylimino)-2,5-cyclohexadien-1-one                                  30   4-(1-naphthylimino)-2,5-cyclohexadien-                                        1-one                                                                    31   4-(2-naphthylimino)-2,5-cyclohexadien-                                        1-one                                                                    32   same as #31                                                              33   same as #29                                                              34   2,5-Bis(phenylamino)-4(phenylimino)-2,5-                                      cyclohexadien-1-one                                                      35   same as #30                                                              36   same as #30                                                              37   2,5-Dibromo-4-[(2,4-dibromophenyl)-                                           imino]-2,5-cyclohexadien-1-one                                           38   same as #37                                                              39   2,3,5-Trichloro-4-[(2,4,6-trichlorophenyl)-                                   imino]-2,5-cyclohexadien-1-one                                           40   2,6-Dichloro-4-[4-[4-(dimethylamino)-                                         phenyl]-5-phenyl-(2H)-imidazol-2-ylidine]-                                    2,5-cyclohexadien-1-one                                                  41   2,6-Dichloro-4-[4,5-bis(4-hydroxyphenyl)-                                     (2H)-imidazol-2-ylidine]-2,5-cyclo-                                           hexadien-1-one                                                           42   2,6-Dimethoxy-4-[4,5-bis(2-furyl)-(2H)-                                       imidazol-2-ylidine]-2,5-cyclohexadien-                                        1-one                                                                    43   2,6-Bis[1,1-(dimethyl)ethyl]-4-[4,5-                                          bis(2-furyl)-(2H)-imidazol-2-ylidene]-2,5-                                    cyclohexadien-1-one                                                      44   4-(phenylimino)-2,5-cyclohexadien-1-imine                                45   same as #44                                                              46   Mono[(3-methyl-2-(3H)-benzothiazol-                                                                   CAS 38901-87-0                                        ylidene)hydrazono]2,5-cyclohexadiene-                                         1,4-dione                                                                47   4-[(3-Chloro-4-oxo-2,5-cyclohexadien-1-                                       ylidine)amino]-1,2-dihydro-1,5-dimethyl-2-                                    phenyl-(3H)-pyrazol-3-one                                                48   4-[(3,5-Dichloro-4-oxo-2,5-cyclohexadien-                                                             CAS 51090-28-9                                        1-ylidine)amino]-1,2-dihydro-1,5-dimethyl-                                    2-phenyl-(3H)-pyrazol-3-one                                              49   3-[(3,5-Dichloro-4-oxo-2,5-cyclohexadien-                                     1-ylidine)amino]-2,5-dihydro-4,5-dimethyl-                                    1-phenylpyrrol-2-one                                                     50   4-(Phenylsulfonyl)imino-1-[4-[(phenyl-                                        sulfonyl)imino]-2,5-cyclohexadien-1-                                          ylidenyl]-2,5-cyclohexadiene                                             51   5-[5-(1,3-Diethylhexahydro-2,4,6-trioxo-5-                                                            CAS 54444-01-8                                        pyrimidinyl)-2,4-pentadienylidene]-1,3-                                       diethyl-2,4,6(1H,3H,5H)-pyrimidenetrione                                      (triethylammonium salt)                                                  52   4-[6,6-Bis[(trifluoromethyl)sulfonyl]-                                                                CAS 58558-78-4                                        1,3,5-hexatrienyl]-N,N-dimethyl-                                              benzenamine                                                              53   4-[4,4-Bis[(trifluoromethyl)sulfonyl]-                                        1,3-butadienyl]-2-ethoxy-N,N-dimethyl-                                        benzenamine                                                              54   4-[4,4-Bis[(trifluoromethyl)sulfonyl]-                                        1,3-butadienyl]-2,5-dimethoxy-N,N-                                            dimethylbenzenamine                                                      55   9-[4,4-Bis[(trifluoromethyl)sulfonyl]-                                                                CAS                                                   1,3-butadienyl]-2,3,6,7-tetrahydro-(1H,5H)-                                                           149679-65-2                                           benzo[ij]quinolizine                                                     56   4-[4,4-Bis[(trifluoromethyl)sulfonyl]-                                        1,3-butadienyl]-2,6-N,N-tetramethyl-                                          benzenamine                                                              57   4-[5,5-Bis[(trifluoromethyl)sulfonyl]-                                        2,4-pentadienylidene]-1,4-dihydro-1-                                          methylquinoline                                                          58   6,6-Bis[4-(dimethylamino)phenyl]1,3,5-                                                                CAS                                                   hexatriene-1,1-bis(sulfonylfluoride)                                                                  149679-82-3                                      59   4-[4,4-Bis[(trifluoromethyl)sulfonyl]-                                                                CAS                                                   1,3-butadienyl]-N,N-dimethylbenzenamine                                                               58559-02-7;                                      60   4-[3-[4-(Dimethylamino)phenyl]-2-                                             propenylidene]-2-phenyl-5(4H)-oxazolone                                  61   2,6-Dichloro-4-[[4-(acetamido)-                                               phenyl]imino]-2,5-cyclohexadien-1-one                                    A    C. I. Disperse Yellow 4; Colour Index                                                                 azo dye                                               12770                                                                    B    C. I. Solvent Yellow 14; Colour Index                                                                 azo dye                                               12055; Sudan Orange R                                                    C    C. I. Solvent Red 24; Colour Index 26105                                                              bis azo dye                                      D    C. I. Solvent Orange 7; Colour Index                                                                  azo dye                                               12140                                                                    E    C. I. Solvent Red 27; Orient Oil Red 5B                                                               bis azo dye                                      F    C. I. Solvent Red 23; Colour Index 26100                                                              bis azo dye                                      G    C. I. Solvent Red 24; Colour Index 26105;                                                             bis azo dye                                           Sudan Red 380                                                            H    C. I. Solvent Red 182; Kayaset Red 802                                                                bis azo dye                                      I    C. I. Solvent Blue 35; Colour Index                                                                   anthraquinone                                         61554; Sudan Blue 670                                                    J    C. I. Solvent Blue 104; Nitrofast Blue 2B                                                             anthraquinone                                    K    C. I. Solvent Blue 36; Colour Index                                                                   anthraquinone                                         61551; Sumiplast Blue OA                                                 L    C. I. Solvent Violet 13; Colour Index                                                                 anthraquinone                                         60725; Oplas Violet 730                                                  M    C. I. Solvent Blue 111; Kayaset Blue 814                                                              anthraquinone                                    N    C. I. Acid Orange 52; Colour Index                                                                    azo dye                                               13025; Methyl Orange                                                     O    C. I. Acid Red 88; Colour Index 15620;                                                                azo dye                                               Fast Red A                                                               P    C. I. Acid Yellow 36; Colour Index                                                                    azo dye                                               13065; Metanil Yellow                                                    Q    C. I. Acid Violet 3; Colour Index                                                                     azo dye                                               16580; Victoria Violet                                                   77   3H-Indolium, 3-[3-[4-(dimethylamino)-                                         phenyl]-2-propenylidene]-1-methyl-2-                                          phenyl, 1,2,2,3,3,4,5,5,6,6-decafluoro-4-                                     (pentafluoroethyl)-cyclohexanesulfonate                                       salt                                                                     78   Benzothiazolium, 3-(3-amino-3-oxo-                                                                    CAS 57230-19-0                                        propyl)-2-[[4-[bis(2-chloroethyl)-                                                                    C. I. Basic                                           amino]phenyl]azo]-6-methoxy-,                                                                         Blue 65;                                              1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                                              Colour                                                fluoroethyl)cyclohexanesulfonate salt                                                                 Index 11076                                      79   Benzothiazolium, 3-(3-amino-3-oxo-                                                                    CAS 12221-38-4                                        propyl)-2-[[4-(diethylamino)-                                                                         C. I. Basic                                           phenyl]azo]-6-ethoxy-, chloride                                                                       Blue 67;                                                                      Colour                                                                        Index 11075                                      80   Benzothiazolium, 3-(3-amino-3-oxo-                                                                    CAS                                                   propyl)-2-[[4-(diethylamino)-2-                                                                       12221-39-5;                                           methylphenyl]azo]-6-ethoxy-,                                                                          Basic blue 87;                                        1,2,2,3,3,4,5,5,6,6-decafluoro-4-                                                                     Colour                                                (pentafluoroethyl)cyclohexanesulfonate                                                                Index 11185                                           salt                                                                     81   CAS 12221-40-8          C. I. Basic                                                                   Blue 68                                          82   CAS 12270-14-3          C. I. Basic                                                                   Blue 76;                                                                      Calcozing                                                                     Blue 2B                                          83   CAS 12221-31-7          C. I. Basic                                                                   Blue 57                                          84   CAS 12221-34-0          C. I. Basic                                                                   Blue 60                                          85   Benzo[a]phenoxazin-7-ium, 9-(dimethyl-                                                                C. I. Basic                                           amino)-, 1,2,2,3,3,4,5,5,6,6-decafluoro-4-                                                            Blue 6;                                               (pentafluoroethyl)-cyclohexanesulfonate                                                               Meldola Blue                                          salt                                                                     86   2-[4,4,-bis[4-dimethylamino)phenyl]-1,3-                                      butadienyl]-1-ethylquinolinium,                                               1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)cyclohexanesulfonate salt                                    87   4-[4,4,-bis[4-(dimethylamino)-                                                                        CAS 80989-42-0                                        phenyl]-1,3-butadienyl]1-ethyl                                                                        (cation)                                              quinolinium, 1,2,2,3,3,4,5,5,6,6-                                             decafluoro-4-(pentafluoroethyl)cyclo-                                         hexanesulfonate salt                                                     88   Naphtho[2,1-d]thiazolium, 2-[4,4-                                             bis[4-(dimethylamino)phenyl]-1,3-                                             butadienyl]-3-ethyl-,1,2,2,3,3,4,5,5,6,6-                                     decafluoro-4-(pentafluoroethyl)cyclo-                                         hexanesulfonate salt                                                     89   2-[2-[4-(dimethylamino)phenyl]ethenyl]-                                       1-phenyl-3-methylquinoxalinium chloride                                  90   Quinolinium, 2-[3-(5-chloro-1,3-dihydro-                                      1,3,3-trimethyl-(2H)-indol-2-ylidene)-1-                                      propenyl]-1-methyl-, 1,2,2,3,3,4,5,5,6,6-                                     decafluoro-4-(pentafluoroethyl)cyclo-                                         hexanesulfonate salt                                                     91   Benzothiazolium, 2-[[4-(dimethylamino)-                                                               C. I. Basic                                           phenyl]azo]-6-methoxy-3-methyl-,                                                                      Blue 54                                               1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)cyclohexanesulfonate salt                                    92   Benz[cd]indolium, 2-[4-(diethylamino)-                                        2-ethoxyphenyl]-1-ethyl-,                                                     1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)-cyclo-hexanesulfonate salt                                  93   2-[p-(Dimethylamino)styryl]-1,3-dimethyl-                                     quinoxalinium methylsulfate salt                                         94   2-[3-(5-chloro-1,3-dihydro-1,3,3-trimethyl-                                   (2H)-indol-2-ylidene)-1-propenyl]-1-                                          methylquinoxalinium, 1,2,2,3,3,4,5,5,6,6-                                     decafluoro-4-(pentafluoroethyl)cyclo-                                         hexanesulfonate salt                                                     95   C. I. Basic Blue 40 (tested as PECH                                                                   Maxilon                                               Sulfonate salt)         Blue RL                                          96   Benzothiazolium, 2-[[4-[ethyl(2-                                                                      C. I. Basic                                           hydroxyethyl)amino]phenyl]azo]-6-                                                                     Blue 41;                                              methoxy-3-methyl-,methylsulfate salt                                                                  Colour                                                                        Index 11105;                                                                  Deorlene Fast                                                                 Blue RL;                                                                      Basacryl Blue                                                                 X-3GL                                            97   Benzothiazolium, 2-[[4-[ethyl(2-                                                                      C. I. Basic                                           hydroxyethyl)amino]phenyl]azo]-6-                                                                     Blue 41;                                              methoxy-3-methyl-, 1,2,2,3,3,4,5,5,6,6-                                                               Colour                                                decafluoro-4-(pentafluoroethyl)cyclo-                                                                 Index 11105,                                          hexanesulfonate salt    Deorlene Fast                                                                 Blue RL;                                                                      Basacryl                                                                      Blue X-3GL                                       98   C. I. Basic Blue 42 (tested as PECH                                           Sulfonate salt)                                                          99   C. I. Basic Blue 53     Basacryl                                                                      Blue 3RL                                         100  3H-Indolium, 5-chloro-2-[5-(5-chloro-                                         1,3-dihydro-1,3,3-trimethyl-2H-indol-2-                                       ylidene)-1,3-pentadienyl]-1,3,3-trimethyl-,                                   1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)-cyclohexanesulfonate salt                                   101  Basic Blue 142                                                           102  Benz[cd]indolium, 2-[2-(9-ethyl-(9H)-                                         carbazol-3-yl)ethenyl]-1-methyl-,                                             1,2,2,3,3,4,5,5,6,6-decafluoro-4-                                             (pentafluoroethyl)cyclohexanesulfonate                                        salt                                                                     104  Benz[cd]indolium, 2-[2-[4-(dimethyl-                                          amino)phenyl]-2-phenylethenyl]-1-methyl-,                                     1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)cyclohexanesulfonate salt                                    105  Benz[cd]indolium, 2-[2,2-bis[4-(dimethyl-                                     amino)phenyl]ethenyl]-1-methyl-, chloride                                     salt                                                                     106  Benz[cd]indolium, 2-[2,2-bis[4-(dimethyl-                                     amino)phenyl]ethenyl]-1-methyl-, iodide                                       salt                                                                     107  Benz[cd]indolium, 2-[2-(2,3-dihydro-1-                                        methyl-2-phenyl-1H-indol-3-yl)-2-(2-                                          methylphenyl)ethenyl]-1-methyl-,                                              1,2,2,3,3,4,5,5,6,6-decafluoro-4-                                             (pentafluoroethyl)cyclohexanesulfonate                                        salt                                                                     108  Pyrimidinium, 4-[5-(2,3-dihydro-1,3-                                          dimethyl-2-oxo-4(1H)-pyrimidinylidene)-                                       1,3-pentadienyl]-2,3-dihydro-1,3-dimethyl-                                    2-oxo-                                                                   109  3H-Indolium, 2-[[3-[(1,3-dihydro-1,3,3-                                       trimethyl-2H-indol-2-ylidene)methyl]-5,5-                                     dimethyl-2-cyclohexen-1-ylidene]methyl]-                                      1,3,3-trimethyl-, 1,2,2,3,3,4,5,5,6,6-deca-                                   fluoro-4-(pentafluoroethyl)cyclohexane-                                       sulfonate salt                                                           110  same as #100                                                             111  Benz[cd]indolium, 2-[2-[4-(diethylamino)-                                     2-methylphenyl]ethenyl]-1-methyl-,                                            1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)cyclohexanesulfonate salt                                    112  3H-Indolium, 3-[3-[4-[(dimethylamino)-                                        phenyl]-2-propenylidene]-1-methyl-2-(4-                                       methoxyphenyl)-, trifluoromethane-                                            sulfonate salt                                                           113  3H-Indolium, 3-[(2,5-dimethyl-1-phenyl-                                       (1H)-pyrrol-3-yl)methylene]-1,2-dimethyl-,                                    trifluoromethanesulfonate salt                                           114  3H-Indolium, 3-[(2,5-dimethyl-1-phenyl-                                       (1H)-pyrrol-3-yl)methylene]-1-methyl-2-                                       phenyl-, trifluoromethanesulfonate salt                                  115  2-[2-[2-chloro-4-(dimethylamino)-                                             phenyl]ethenyl]-1-methylbenz[cd]indolium,                                     1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)-cyclohexanesulfonate salt                                   116  same as #77                                                              117  C. I. Basic Violet 22 (tested as PECH                                                                 Basacryl                                              Sulfonate salt)         Violet RL                                        118  C. I. Basic Red 15 (tested as PECH                                                                    Genacryl                                              Sulfonate salt)         Brilliant                                                                     Red B                                            119  same as #94                                                              120  same as #111                                                             121  Benz[cd]indolium, 2-[2-[4-(dimethyl-                                          amino)phenyl]ethenyl]-1-methyl-,                                              1,2,2,3,3,4,5,5,6,6-decafluoro-4-(penta-                                      fluoroethyl)-cyclohexanesulfonate salt                                   122  Benz[cd]indolium,2-[2-[4-(dimethylamino)-                                     2-ethoxyphenyl]ethenyl]-1-methyl, iodide                                      salt                                                                     123  3H-Indolium, 2-[1-cyano-4,4-bis[4-                                            (dimethylamino)phenyl]-1,3-butadienyl]-                                       1,3,3-trimethyl-, 1,2,2,3,3,4,5,5,6,6-                                        decafluoro-4-(penta-fluoroethyl)-cyclo-                                       hexanesulfonate salt                                                     ______________________________________                                    

                  TABLE 1b                                                        ______________________________________                                                Gel                 Solu-                                                     time  Color Change  bility                                            Dye  Initial  (sec-   at 2 ×                                                                         at     in sili-                                                                            Color                               #    Color    onds)   GT.sup.3                                                                             24 hours                                                                             cone.sup.2                                                                          Change                              ______________________________________                                        1    purple   265     bleached                                                                             bleached                                                                             S     +                                   2    blue     290     bleached                                                                             bleached                                                                             S     +                                                         (light                                                                        yellow)                                                 3    blue     320     bleached                                                                             bleached                                                                             S     +                                                         (light                                                                        yellow)                                                 4    blue     320     bleached                                                                             bleached                                                                             SS    +                                                         (light                                                                        yellow)                                                 5    blue     245     bleached                                                                             bleached                                                                             S     +                                   6    blue     217     bleached                                                                             bleached                                                                             S     +                                   7    blue     250     bleached                                                                             bleached                                                                             I                                         8    purple   267     bleached                                                                             bleached                                                                             S     +                                   9    purple   305     bleached                                                                             bleached                                                                             S     +                                   10   blue     293     bleached                                                                             bleached                                                                             I                                         11   purple   255     no     bleached                                                               change                                                  12   blue/    270     bleached                                                                             bleached                                                                             S     +                                        green                                                                    13   blue     230     bleached                                                                             bleached                                                                             I                                         14   aqua     288     no     bleached                                                                             I                                                               change                                                  15   green    240     bleached                                                                             bleached                                                                             S     +                                   16   blue     505     bleached                                                                             bleached                                                                             S     +                                                         before                                                                        gel                                                     17   green    282     partially                                                                            bleached                                                               bleached                                                18   purple   277     no     bleached                                                               change                                                  19   purple   284     no     bleached                                                               change                                                  20   orange   257     partially                                                                            bleached                                                                             I                                                               bleached                                                21   blue     270     partially                                                                            bleached                                                                             S     +                                                         bleached                                                22   lavender 240     bleached                                                                             bleached                                                                             I                                         23   purple   261     bleached                                                                             bleached                                                                             S     +                                   24   purple   290     no     bleached                                                               change                                                  25   blue     330     partially                                                                            bleached                                                               bleached                                                26   purple   335     no     bleached                                                               change                                                  27   purple   420     no     bleached                                                               change                                                  28   purple   330     color  bleached                                                                             I                                                               changed                                                 29   orange   246     bleached                                                                             bleached                                                                             SS                                        30   magenta  270     bleached                                                                             bleached                                                                             S     +                                   31   orange   264     bleached                                                                             bleached                                                                             S     +                                   32   orange   333     bleached                                                                             bleached                                                                             S     +                                   33   orange   330     bleached                                                                             bleached                                                                             S     +                                   34   orange   240     bleached                                                                             bleached                                                                             S     +                                   35   orange   240     bleached                                                                             bleached                                                                             S     +                                   36   magenta  270     bleached                                                                             bleached                                         37   magenta  600     no     bleached                                                               change                                                  38   orange   240     no     bleached                                                               change                                                  39   red, low 270     bleached                                                                             bleached                                              intes.                                                                   40   blue/    290     slight bleached                                                                             I                                              green            bleaching                                               41   orange   250     slight bleached                                                                             S     slight                                                    bleaching           bleaching                           42   magenta  317     bleached                                                                             bleached                                                                             S     slight                                                                        bleaching                           43   orange   240     no     bleached                                                               change                                                  44   orange   250     bleached                                                                             bleached                                                                             I                                         45   orange   450     no     bleached                                                                             S     slight                                                    change              bleaching                           46   orange   241     bleached                                                                             bleached                                                                             S     slight                                                                        bleaching                           47   orange   258     bleached                                                                             bleached                                                                             SS                                        48   magenta  260     no     bleached                                                                             S     no                                                        change              change                              49   orange   227     bleached                                                                             bleached                                                                             S     slight                              50   orange   240     bleached                                                                             bleached                                         51   fluor.   246     bleached                                                                             bleached                                                                             S     +                                        blue                                                                     52   purple   330     bleached                                                                             bleached                                                                             S     +                                   53   purple/  313     bleached                                                                             bleached                                                                             S     +                                        pink                                                                     54   purple/  310     bleached                                                                             bleached                                                                             S     +                                        pink                                                                     55   purple   326     bleached                                                                             bleached                                                                             SS    +                                   56   purple   332     bleached                                                                             bleached                                                                             SS    +                                   57   purple   310     bleached                                                                             bleached                                                                             SS    +                                   58   blue     258     bleached                                                                             bleached                                                                             S     +                                   59   magenta  306     bleached                                                                             bleached                                                                             S                                         60   magenta  313     bleached                                                                             bleached                                                                             SS                                        61   lavender 315     not    bleached                                                                             S     +                                                         measured      (in-                                                                          tense)                                    A    yellow   270     no                                                                            change                                                  B    orange   290     no     no                                                                     change change                                           C    red      298     no     no                                                                     change change                                           D    orange   276     no     no                                                                     change change                                           E    red      212     no     slight                                                                 change                                                  F    red      194     slight darker                                                                 darken-                                                                       ing                                                     G    red      247     no     no                                                                     change change                                           H    red      80      no                                                                            change                                                  I    blue     377     no     no                                                                     change change                                           J    blue     237     no     no                                                                     change change                                           K    blue     103     no                                                                            change                                                  L    blue     90      no                                                                            change                                                  M    blue     81      no                                                                            change                                                  N    orange   300     no     slight                                                                 change bleaching                                        O    lavender 235     no     no                                                                     change change                                           P    yellow   270     no     no                                                                     change change                                           Q    purple   291     no     no                                                                     change change                                           77   blue     150     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                78   blue     219     bleached                                                                             bleached                                                                             I                                         79   blue     261     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                80   blue     259     bleached                                                                             bleached                                                                             I                                         81   purple   256     bleached                                                                             bleached                                                                             I                                         82   blue     236     bleached                                                                             bleached                                                                             I                                         83   blue     266     bleached                                                                             bleached                                                                             I                                         84   blue     290     bleached                                                                             bleached                                                                             I                                         85   purple   182     bleached                                                                             bleached                                                                             I                                         86   blue     270     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                87   blue     380     bleached                                                                             bleached                                                                             I                                         88   blue     360     bleached                                                                             bleached                                                               before                                                                        gel time                                                89   blue     255     bleached                                                                             bleached                                                                             I                                         90   blue     205     bleached                                                                             bleached                                                                             I                                         91   blue     246     bleached                                                                             bleached                                                                             I                                         92   blue     267     partially                                                                            bleached                                                                             I                                                               bleached                                                93   blue     232     bleached                                                                             bleached                                                                             I                                         94   blue     240     bleached                                                                             bleached                                                                             I                                         95   blue     220     bleached                                                                             bleached                                                                             I                                         96   purple   164     bleached                                                                             bleached                                                                             I                                         97   purple   193     bleached                                                                             bleached                                                                             I                                         98   purple   196     bleached                                                                             bleached                                                                             I                                         99   blue     278     bleached                                                                             bleached                                                                             I                                         100  blue     258     bleached                                                                             bleached                                                                             I                                         101  blue     287     bleached                                                                             bleached                                                                             I                                         102  blue     320     bleached                                                                             bleached                                                                             I                                         104  green    252     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                105  green    252     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                106  blue/    370     bleached                                                                             bleached                                                                             I                                              green            before                                                                        gel time                                                107  green    600     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                108  blue     290     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                109  purple   166     bleached                                                                             bleached                                                                             I                                         110  blue     582     bleached                                                                             bleached                                                                             I                                         111  blue/    368     bleached                                                                             bleached                                                                             I                                              green            before                                                                        gel time                                                112  blue     278     bleached                                                                             bleached                                                                             I                                         113  orange   371     bleached                                                                             bleached                                                                             I                                         114  orange   260     bleached                                                                             bleached                                                                             I                                         115  green/   409     bleached                                                                             bleached                                                                             I                                              blue                                                                     116  blue     955     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                117  magenta  337     bleached                                                                             bleached                                                                             I                                         118  magenta  337     bleached                                                                             bleached                                                                             I                                         119  magenta  283     bleached                                                                             bleached                                                                             I                                         120  blue/    155     bleached                                                                             bleached                                                                             I                                              green            before                                                                        gel time                                                121  blue     222     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                122  purple   204     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                123  purple   190     bleached                                                                             bleached                                                                             I                                                               before                                                                        gel time                                                ______________________________________                                         Footnotes for Tables 1a and 1b:                                               .sup.1 The "dye #" and "identification" correspond to the formula depicte     in the attached drawings of dye structures. For brevity, the "dye #"          listed in Table 1a will be used throughout the examples to refer to           specific dyes. Notably, the cationic dyes may comprise any suitable           counter ion and are not limited to the specific counter ion(s) shown or       depicted in the table or the attached drawings. Similarly, anionic dyes       may comprise any suitable counter ion and are not limited to the specific     counter ion(s) shown or depicted in the table or the attached drawings.       Cationic dyes #77, 78, 80, 85-88, 90-92, 94-95, 97-98, 100, 102, 104, 107     109-111, 115-121, and 123 were tested as PECH Sulfonate salts, though the     CAS # or C. I. name or number listed in the table may describe the cation     paired with a different anion.                                                .sup.2 "S" = soluble; "I" = insoluble; "SS" = slightly soluble.               .sup.3 "2 × GT" = twice the time elapsed to gel time.                   .sup.4 "PECH Sulfonate" =                                                     1,2,2,3,3,4,5,5,6,6decafluoro-4-(pentafluoroethyl)cyclohexane sulfonate. 

The data of Table 1b show that neutral dyes 1 to 50 and 52 to 61,anionic dye 51, and cationic dyes 77 to 123 all exhibit a significantcolor change within 24 hours. Notably, dye 51 changed from being afluorescent dye to a colorless non-fluorescent dye. In addition, many ofthese dyes exhibit a color change at some time less than two times thegel point ("2×GT"). Several dyes (e.g., 16, 77, 79, 86, 88, 104-108,111, 116, and 120-123) exhibited bleaching prior to gelation and may besuitable as working time indicators. Dyes potentially suitable as settime indicators include: neutral dyes 1-10, 12-13, 15, 17, 22, 23,29-36, 39, 42, 44, 46, 47, 49-50, 52-60, anionic dye 51, and cationicdyes 78, 80-85, 87, 89-102, 109, 110, 112-115, and 117-119.

In contrast, comparison dyes A to E and G to Q comprising neutral azoand anthraquinone dyes fail to exhibit a significant color change duringany stage of the curing process. Comparison dye F exhibited a gradualdarkening over 24 hours that did not correlate to any particular curingstate.

Example 2

A number of dyes were further examined for solubility in the solventlesssilicone formulations of Preparatory Example 2. Those dyes thatexhibited a noticeable color change within two times the gel point (asobserved in Example 1) were evaluated for silicone solubility by thefollowing procedure. Approximately 500 μg of the dye was transferred toa 1.5 dram (6 ml) glass vial. Approximately 1 ml of stock composition B1was transferred to the vial with a disposable dropper, the solution wasmixed with a spatula for approximately 3 minutes, and the mixture wasexamined visually for coloration of the silicone liquid. Coloration ofthe resin indicates that the dye was soluble or highly dispersed in thecomposition. Several dyes required 1 to 2 drops (˜150 to 300 mg) ofdichloromethane to induce solubility and were classified as "slightlysoluble". Those dyes that required additional solvent (i.e., more than1-2 drops) to color the composition were classified as "insoluble". Thedata is presented in Table 1b. Neutral dyes 1-6, 8-9, 12, 15, 16, 21,23, 29-35, 41, 42, 45-49, 52-55, 57-59, and 61, and anionic dye 51 wereall at least slightly soluble in stock composition B1. None of thecationic dyes were soluble in stock composition B1, although it isbelieved presently that such solubility could be achieved by modifyingthe anion, by modifying the dye cation (e.g., by incorporating asuitable solubilizing group), or perhaps by modifying the dye cation toprovide an amphoteric dye.

Example 3

A variety of silicone soluble dyes were evaluated as "cure indicators"in solventless silicone formulations. Neutral dyes 1-6, 8-9, 12, 15, 16,21, 23, 30-35, 41, 42, 45, 46, 48, 49, 52-58, and 61, and anionic dye 51were independently evaluated in the following procedure. Approximately500 μg of a dye was transferred to a 1.5 dram (6 ml) glass vial. To thiswas added approximately 1 ml of stock composition B1, e.g., using adisposable dropper, the solution was mixed with a spatula forapproximately 3 minutes and the mixture was examined visually forcoloration of the resin and general solubility of the dye.Dichloromethane was used sparingly (1-2 drops) to promote solubility ofless-soluble dyes. Approximately 1 ml of stock composition C1 wastransferred to the colored solution, a timer was started and thecomposition was mixed thoroughly with a mixing stick for 30 seconds. Thecomposition was placed against a white background and examined for thetimes at which gelation and visual color change occurred, andspecifically if a color change occurred before the gel point, or withintwo times the gel point at room temperature. The data in Table 1b showsthat nearly all of these dyes examined exhibited a partial or totalcolor change within two times the gel point.

Example 4

A simple and effective method of selecting suitable cure-indicating dyesfor compositions of this invention was developed and a variety of dyeswere evaluated by this method. Dyes were evaluated according to thefollowing "pentamethyldisiloxane test". Approximately 500 μg of dye wastransferred to a 1.5 dram (6 ml) clear-glass, screw cap vial. To thiswas added, in order, 500 μl of dichloromethane, 100 μl ofpentamethyldisiloxane, and either: (A) 25 μl of a catalyst solutioncomprising 25% by weight of a commercially available catalyst (PC₀₇₅,available frown United Chemical Technology, Inc. Bristol, Pa.) indichloromethane; or (B) 10 μl of a commercially available catalystsolution (PC₀₇₂, available from United Chemical Technology, Inc.Bristol, Pa.). The vial was capped, agitated for approximately 5 secondsat room temperature and the solution was observed for bleaching. Thosedyes that exhibited bleaching within 5 minutes also exhibited asignificant color change in the compositions of Example 1 and arebelieved to be suitable for use in this invention. Set out below inTable 4a are the dye number, dye type, results of the reactivity testand corresponding color change results from Table 1b. The data fromTable 4a shows that dyes that fail to exhibit a significant color changein the reactivity test (indicated with a negative sign "-") are unlikelyto function as visible cure monitors for the compositions of thisinvention; whereas, those dyes exhibiting a positive test response(indicated with a positive sign "+") are likely to serve as effectivecure monitors. Notably, of the neutral anthraquinone and azo dyestested, all failed the reactivity test and were ineffective curemonitors in the formulations of Example 1.

                  TABLE 4a                                                        ______________________________________                                        Comparison of Reactivity Test Results and Example 1 Results                   Dye              Reactivity Test                                                                           Table 1b Color Change                            Number Dye Type  Results     Results                                          ______________________________________                                         1     neutral   +           +                                                 2     neutral   +           +                                                 4     neutral   +           +                                                16     neutral   +           +                                                52     neutral   +           +                                                59     neutral   +           +                                                60     neutral   +           +                                                77     cationic  +           +                                                78     cationic  +           +                                                82     cationic  +           +                                                91     cationic  +           +                                                96     cationic  +           +                                                97     cationic  +           +                                                99     cationic  +           +                                                101    cationic  +           +                                                B      neutral   -           -                                                C      neutral   -           -                                                D      neutral   -           -                                                E      neutral   -           -                                                F      neutral   -           -                                                G      neutral   -           -                                                H      neutral   -           -                                                I      neutral   -           -                                                J      neutral   -           -                                                K      neutral   -           -                                                L      neutral   -           -                                                M      neutral   -           -                                                N      neutral   -           -                                                O      neutral   -           -                                                P      neutral   -           -                                                Q      neutral   -           -                                                ______________________________________                                    

Example 5

A stock hydride and dye composition (H5) was prepared by combining andmixing in a glass container 0.0035 parts by weight of dye number 2 and50 parts by weight of the crosslinker compound of Preparatory Example 2("XL1").

A stock vinyl and dye composition (V5) was prepared by combining andmixing in a glass container 0.0035 parts by weight of dye number 2 and50 parts by weight of the vinyl terminated polydimethylsiloxane compoundof Preparatory Example 2 ("LMWP").

A stock catalyst composition (C5) was prepared by combining and mixingin a glass container 5 parts by weight of the platinum catalyst solutiondescribed in Preparatory Example 2 and 5 parts by weightdichloromethane.

Five compositions comprising varying hydride/vinyl ratios were preparedaccording to the following procedure and evaluated for gelation and dyecolor bleaching. Ten grams of V5 was transferred to each of five glassvials along with 0.20, 0.30, 0.40, 0.50, and 0.60 grams respectively ofH5. The compositions were mixed thoroughly, 0.10 grams of C5 was addedto each vial, and the compositions again mixed until homogeneous. Thesamples were examined after standing 5 minutes and also after standingapproximately 1 hour, and a determination of gelation and bleachingestablished. Set out below in Table 3 are the run number, proportions ofH5, V5, and C5, approximate ratio of hydride to vinyl, and whethergelation and/or bleaching occurred following 5 and 60 minutes. The datashows that gelation occurs for all compositions (indicated as "+" sign)whereas complete bleaching (indicated as "+" sign) only occurs when theratio of hydride to vinyl exceeds approximately one. Samples having aratio of hydride to vinyl less than approximately one did not bleach(indicated as "-" sign). This result indicates that under the conditionsof this example excess (i.e., unreacted) hydride is required to effectbleaching of the dye and that the reaction between hydride and vinyloccurs preferentially to the reaction between hydride and dye.

                  TABLE 5a                                                        ______________________________________                                                       Hydride:      Bleaching                                             H5      V5      C5    vinyl       at 5  at 60                            Run  (gms)   (gms)   (gms) ratio  Gel  min   min                              ______________________________________                                        1    0.20    10.0    0.10  0.50   +    -     -                                2    0.30    10.0    0.10  0.75   +    -     -                                3    0.40    10.0    0.10  1.00   +    slight                                                                              slight                                                                  bleach-                                                                             bleach-                                                                 ing   ing                              4    0.50    10.0    0.10  1.25   +    +     +                                5    0.60    10.0    0.10  1.50   +    +     +                                ______________________________________                                    

Example 6

A filled molding or dental impression material composition was preparedaccording to the following procedure. A filled base composition (B6) wasprepared by transferring 25 parts by weight each of stock composition B1from Preparatory Example 2 and dichloromethane to a 225 ml Semco mixingtube (available from Technical Resin Packaging Inc., Brooklyn Park,Minn.) and agitated by shaking. 0.0034 grams of dye #77 was dissolved in1.2 grams of dichloromethane, added to the Semco cartridge and mixed byshaking. Ten grams of Quso WR-55 filler (available from Degussa Corp.,Dublin, Ohio) was added to the cartridge and mixed 5 minutes on a Model388 automatic Semkit Mixer (available from Technical Resin PackagingInc., Brooklyn Park, Minn.). 50.0 grams of Imsil A-25 filler (availablefrom Micronized Unimen Specialty Minerals, Cairo, Ill. as Imsil A-25micro crystalline silica) was then added to the cartridge and mixed for10 minutes. Finally, an additional 5 grams each of B1 anddichloromethane was added to the cartridge and mixed for 5 minutesyielding a light blue paste.

A filled catalyst composition (C6) was prepared by transferring 25 partsby weight each of stock composition C1 from Preparatory Example 2 anddichloromethane to a 225 ml Semco mixing tube and agitated by shaking.8.3 grams of Quso filler was added to the tube, mixed 5 minutes on amodel 388 Semkit Mixer, followed by the addition of 41.7 grams of ImsilA-25 filler and 12 minutes mixing. This procedure yielded a white paste.

Approximately equal volumes of B6 and C6 were transferred to independentchambers of a dual barrel mixing cartridge which were sealed withinserts. The cartridge was inserted into a hand held dispensingapparatus, a Kenics static mixing tip was placed on the cartridge, andthe catalyst (C1) and base (B1) mixed by co-extrusion through the mixingtip. A Kenics static mixer consists of a circular pipe within which arefixed a series of short helical elements of alternating left- andright-hand pitch. The helical design of the central element causes atransverse flow to arise in the plane normal to the pipe axis. As aconsequence, radial mixing of the two compositions is achieved. Acomplete description of the fluid mechanics of a Kenics static mixer maybe found on pages 327 and 328 of Fundamentals of Polymer Processing, byStanley Middleman. The silicone compound begins to react (i.e.,crosslink) upon mixing the two compositions together.

The mixed paste became rigid and exhibited a color change from lightblue to pale blue within about 6 minutes.

Example 7

A solventless, filled, molding or dental impression material compositionwas prepared according to the following procedure. A filled basecomposition (B7) was prepared by transferring 200 grams of stockcomposition B1 from Preparatory Example 2, 2.8 grams Silwet L-77(available from OSi Specialties, Inc., Lisle, Ill.), and 20 grams QusoWR-55 to a Ross double planetary mixer. The materials were mixed for 5minutes at 40 rpm. 135 grams of Imsil A-25 filler were then added to themixer pot and mixed for 5 minutes. Finally, 45.0 grams of Imsil A-25were added to the mixer and mixed under vacuum for 35 minutes yielding awhite paste.

A filled catalyst composition (C7) was prepared by dissolving in a Rossmixer approximately 0.0254 grams of dye #2 in 187 grams of stockcomposition C1 from Preparatory Example 2. 2.62 grams Silwet L-77 and18.7 grams Quso WR-55 were added to the Ross mixer and mixed for 5minutes at 40 rpm. A 126 gram aliquot of Imsil A-25 filler was added tothe mixer, mixed for 5 minutes followed by the addition of an additional42 grams of Imsil A-25 and mixing for 35 minutes under vacuum at 40 rpm.This process yielded a blue catalyst paste.

Approximately equal volumes of B7 and C7 were transferred to independentchambers of a dual-barrel mixing cartridge. The cartridge was insertedinto a hand-held dispensing apparatus, a static-mixing tip placed on thecartridge and the catalyst (C7) and base (B7) mixed by co-extrusionthrough the static-mixing tip. The mixed paste stiffened, then becamerigid and exhibited a color change from light blue to white atapproximately the same time of 3 to 3.5 minutes.

Example 8

The effects of varying levels of hydride/vinyl ratio, vinyl/platinumratio and dye concentration upon bleaching time and setting time wereexamined by utilizing a three-variable "central composite" designexperiment. Experiments of this type are extremely useful in examiningthe effects of reactive ingredients and optimizing the compositionformula to prepare practical, useful impression materials.

As shown in Table 8a, catalyst impression materials (C8) wereindividually prepared by adding the indicated parts by weight ofplatinum catalyst (a solution of 2.55% Pt by weight in vinyl-terminatedpolydimethylsiloxane as described in Preparatory Example 1),vinyl-terminated polydimethylsiloxane ("LMWP" as described inPreparatory Example 2) and Aerosil R202 (a fumed silica available fromDegussa Corp., Dublin, Ohio) to a 225 ml Semco tube and mixing by meansof a model 388 Semkit mixer for 7 minutes. Base impression materials(C8) were prepared similarly by adding the indicated parts by weight ofcrosslinker ("XL1" as described in Preparatory Example 2),vinyl-terminated polydimethylsiloxane "LMWP", dye #2 (added as a 0.05w/w solution in CHCl₃), and Aerosil R202 to a 225 ml Semco tube andmixing by means of a model 388 Semkit mixer for 7 minutes.

Approximately equal volumes of C8 and B8 were added to independentchambers of a dual-barrel mixing cartridge and mixed by extrudingthrough a static-mixing element. Curing parameters were determined on aMonsanto Model R100 oscillating disc rheometer and are presented inTable 8b. The rheometer measures torque as a function of time. "T5" isthe amount of time it takes for the torque to reach 5% of maximum value."T90" is the amount of time it takes for the torque to reach 90% ofmaximum value. These values approximate the working time and settingtime of the composition, respectively.

Table 8b shows cure times (T90 and T5) and bleach time (BT) at 27° C.for each sample. The SiH/Vinyl ratio, Vinyl/Pt ratio, and dyeconcentration were all found to be significant contributors to thebleach time. It is especially useful to examine the data with referenceto the bleach time and BT/T90 ratio. The SiH/Vinyl ratio was the mostsignificant variable (i.e., had the strongest effect on BT). Runs #1, 3,5, 7, and 13 all have SiH/Vinyl less than 1.0. Notably, bleaching wasobserved only for run #3 (which had low dye concentration and a highVinyl/Pt ratio).

By examining selected pairs of runs one can determine the effect ofindividual variables. For example, comparing run #2 to #4, run #6 to #8,or run #15 to #16 one can isolate the effect of changing the vinyl/Ptratio. In general, increasing the amount of Pt decreases both BT and theBT/T90 ratio. By comparing run #2 to #6, run #4 to #8, or run #17 to #18one can isolate the effect of dye concentration. In general, raising thedye concentration increases the BT and BT/T90 ratio.

The BT/T90 ratio is indicative of the relationship between setting timeand bleaching time. Setting time indicator compositions may begeneralized to those materials having a BT/T90 ratio of approximately1.0. Compositions with BT/T90 ratios greater than about 1.2 may haveless utility in this application. Compositions with a BT/T5 ratio ofapproximately 1.0 may be viable working time indicators.

                                      TABLE 8a                                    __________________________________________________________________________    Catalyst Paste (parts)                                                                           Base Paste (parts)                                                 Vinyl          Vinyl                                                          terminated     terminated                                                     polydimethyl-                                                                        Aerosil                                                                           Cross-                                                                            polydimethyl                                                                              Aerosil                                    Run                                                                              Catalyst                                                                           siloxane                                                                             R202                                                                              linker                                                                            siloxane                                                                             Dye #2                                                                             R202                                       __________________________________________________________________________    1  0.0148                                                                             49.985 5   3.65                                                                              46.35  0.00061                                                                            5                                          2  0.013                                                                              49.987 5   15.4                                                                              34.6   0.00061                                                                            5                                          3  0.0931                                                                             49.907 5   3.64                                                                              46.36  0.00061                                                                            5                                          4  0.0819                                                                             49.918 5   15.39                                                                             34.61  0.00061                                                                            5                                          5  0.0148                                                                             49.985 5   3.65                                                                              46.35  0.01020                                                                            5                                          6  0.013                                                                              49.987 5   15.4                                                                              34.6   0.01020                                                                            5                                          7  0.0931                                                                             49.907 5   3.64                                                                              46.36  0.01020                                                                            5                                          8  0.0819                                                                             49.918 5   15.39                                                                             34.61  0.01020                                                                            5                                          9  0.0357                                                                             49.964 5   7.66                                                                              42.34  0.00250                                                                            5                                          10 0.0357                                                                             49.964 5   7.66                                                                              42.34  0.00250                                                                            5                                          11 0.0357                                                                             49.964 5   7.66                                                                              42.34  0.00250                                                                            5                                          12 0.0357                                                                             49.964 5   7.66                                                                              42.34  0.00250                                                                            5                                          13 0.0377                                                                             49.962 5   2.25                                                                              47.75  0.00250                                                                            5                                          14 0.0297                                                                             49.97  5   23.03                                                                             26.97  0.00250                                                                            5                                          15 0.00795                                                                            49.99  5   7.66                                                                              42.34  0.00250                                                                            5                                          16 0.1596                                                                             49.84  5   7.65                                                                              42.35  0.00250                                                                            5                                          17 0.0357                                                                             49.964 5   7.66                                                                              42.34  0.00025                                                                            5                                          18 0.0357                                                                             49.964 5   7.66                                                                              42.34  0.02500                                                                            5                                          19 0.0357                                                                             49.964 5   7.66                                                                              42.34  0.00250                                                                            5                                          20 0.0357                                                                             49.964 5   7.66                                                                              42.34  0.00250                                                                            5                                          __________________________________________________________________________

                                      TABLE 8b                                    __________________________________________________________________________       SiH/                                                                             Si-Vi/    Bleach                                                                              T90                                                                              T5 Bleach                                                                              Bleach                                      Run                                                                              Si-Vi                                                                            Pt  Dye, grams                                                                          Time (sec)                                                                          (sec)                                                                            (sec)                                                                            Time/T90                                                                            Time/T5                                     __________________________________________________________________________    1  0.82                                                                             112.4                                                                             0.00061                                                                             >10,000                                                                             586                                                                              259                                                                              >20   >40                                         2  3.95                                                                             112.4                                                                             0.00061                                                                             82    114                                                                               85                                                                              0.72  0.96                                        3  0.82                                                                             17.9                                                                              0.00061                                                                             160   371                                                                              164                                                                              0.43  0.98                                        4  3.95                                                                             17.9                                                                              0.00061                                                                             52     82                                                                               45                                                                              0.63  1.16                                        5  0.82                                                                             112.4                                                                             0.01020                                                                             >10,000                                                                             552                                                                              240                                                                              >20   >40                                         6  3.95                                                                             112.4                                                                             0.01020                                                                             110    94                                                                               59                                                                              1.17  1.86                                        7  0.82                                                                             17.9                                                                              0.01020                                                                             >10,000                                                                             354                                                                              153                                                                              >30   >60                                         8  3.95                                                                             17.9                                                                              0.01020                                                                             70     82                                                                               45                                                                              0.85  1.56                                        9  1.8                                                                              44.8                                                                              0.00250                                                                             174   178                                                                              109                                                                              0.98  1.60                                        10 1.8                                                                              44.8                                                                              0.00250                                                                             164   191                                                                              114                                                                              0.86  1.44                                        11 1.8                                                                              44.8                                                                              0.00250                                                                             167   178                                                                              110                                                                              0.94  1.52                                        12 1.8                                                                              44.8                                                                              0.00250                                                                             170   189                                                                              113                                                                              0.9   1.50                                        13 0.5                                                                              44.8                                                                              0.00250                                                                             >10,000                                                                             411                                                                              250                                                                              >25   >40                                         14 6.5                                                                              44.8                                                                              0.00250                                                                             39     52                                                                               32                                                                              0.75  1.22                                        15 1.8                                                                              201 0.00250                                                                             272   273                                                                              147                                                                                1   1.85                                        16 1.8                                                                              10  0.00250                                                                             102   162                                                                               85                                                                              0.63  1.20                                        17 1.8                                                                              44.8                                                                              0.00025                                                                             136   175                                                                              108                                                                              0.78  1.26                                        18 1.8                                                                              44.8                                                                              0.02500                                                                             232   180                                                                              111                                                                              1.29  2.09                                        19 1.8                                                                              44.8                                                                              0.00250                                                                             160   182                                                                              112                                                                              0.88  1.43                                        20 1.8                                                                              44.8                                                                              0.00250                                                                             187   176                                                                              109                                                                              1.06  1.72                                        __________________________________________________________________________

Example 9

Several other dyes evaluated in Examples 1 and 4 were compounded intofilled molding or dental impression material compositions according tothe following procedure.

Filled catalyst compositions (C9) were prepared by adding 0.014 parts ofdye dissolved in 0.7 ml of CHCl₃ to a stock catalyst solution containing96.73 parts vinyl-terminated polydimethylsiloxane ("LMWP" fromPreparatory Example 2), 0.76 parts Silwet L-77, and 2.51 parts platinumcatalyst ("Karstedt" type Pt catalyst, 2 to 3% Pt invinyldimethylsiloxy-terminated polydimethylsiloxane, prepared in asimilar manner as described in Preparatory Example 1a and having aviscosity of 2.0 Pa s.) in an 225 ml Semco tube. 10 parts Quso WR-55were added and mixed by means of a model 388 Semkit mixer for 5 minutes.60 parts Imsil A-25 were added and mixed for 5 minutes followed by 30parts Imsil A-25 and mixing for an additional 30 minutes to yieldcolored pastes.

Filled base compositions (B9a and B9b) were prepared by the followingprocedure. B9a: 178 parts crosslinker ("XL1"), 620 parts vinylterminated polydimethylsiloxane ("LMWP"), 11.2 parts Silwet L-77, and 80parts Quso WR-55 were added to a 1 gallon Ross mixer and mixed for 5minutes at 30 rpm. 480 parts Imsil A-25 were added and mixed for 5minutes at 30 rpm. Finally, 240 parts Imsil A-25 were added and mixedunder vacuum for 50 minutes at 30 rpm to yield an off-white paste. B9b:66 parts crosslinker ("XL1"), 231 parts vinyl terminatedpolydimethylsiloxane ("LMWP"), 4.2 parts Silwet L-77, and 30 parts QusoWR-55 were added to a 1 quart Ross mixer and mixed 5 minutes at 40 rpm.179 parts Imsil A-25 were added and mixed for 5 minutes at 40 rpm.Finally, 90 parts Imsil A-25 were added and mixed for 50 minutes undervacuum at 40 rpm to yield an off-white paste.

Approximately equal volumes of C9 and B9a (runs 1, 2, and 6-10) or C9and B9b (runs 3-5) were placed in the chambers of a dual-barrel mixingcartridge and mixed by extruding through a static-mixing element. Themixed pastes cured in approximately 3 to 3.5 minutes (cure time definedas T90 at 27° C.). The bleach times, defined as the amount of time ittakes to bleach completely (as compared to a reference prepared withoutdye) are listed in Table 9a below.

                  TABLE 9a                                                        ______________________________________                                                                      Bleach Time                                     Run    Dye         Initial Color                                                                            (80° F.)                                 ______________________________________                                        1      none        off white  NA                                              2      #2          blue       4 minutes                                       3      #53         pink       5 minutes                                       4      #60         purple     6 minutes                                       5      #56         pink       4 minutes                                       6      H           pink       DNBC.sup.1                                      7      E           pink       DNBC.sup.1                                      8      L           purple     DNB.sup.2                                       9      K           blue       DNB.sup.2                                       10     M           blue       DNB.sup.2                                       ______________________________________                                         Footnotes for Table 9a:                                                       .sup.1 Approximately 80-90% bleaching occurred in 90-120 minutes; however     the sample did not bleach completely ("DNBC") even after 72 hours.            .sup.2 "DNB" = did not bleach.                                           

Example 10

Several other filled molding or dental impression compositions wereprepared utilizing dye #2 and also a non-cure-indicating pigment toimpart both a unique initial-mix and final-cure colors.

Cure-indicating base impression material composition (B10) was preparedby adding 22.4 parts Silwet L-77, 356 parts crosslinker ("XL1"), 1239parts vinyl terminated polydimethylsiloxane ("LMWP"), and 0.23 parts dye#2 (added as a 0.05 w/w solution in CHCl₃) to a Ross mixer and mixing 5minutes at 30 rpm. 160 parts Quso WR-55 were then added and mixed for 5minutes at 30 rpm. 960 parts Imsil A-25 were added and mixed for 5minutes at 30 rpm followed by 480 parts Imsil A-25 and an additional 50minutes mixing at 30 rpm under vacuum to yield a blue base impressionpaste.

Catalyst impression material compositions (C10) were prepared by adding11.2 parts Silwet L-77, 783 parts vinyl terminated polydimethylsiloxane("LMWP"), 16.4 parts Pt catalyst (as described in Preparatory Example 1abut diluted in "LMWP"), and either 8 parts of red pigment (availablefrom Warner-Jenkinson, St. Louis, Mo. as #K7183 D&C Red #7 Calcium Lake)or 16 parts of yellow pigment (available from Reed Spectrum, Inc.,Minneapolis, Minn. as Yellow #1604404) to a Ross mixer and mixing for 5minutes at 30 rpm. 80 parts Quso WR-55 was added and mixed 5 minutes at30 rpm. 480 parts Imsil A-25 were added and mixed for 5 minutes at 30rpm followed by 240 parts Imsil A-25 and an additional 50 minutes mixingat 30 rpm under vacuum to yield pinkish-red (C10a) or yellow (C10b)catalyst impression pastes.

Approximately equal volumes of C10 and B10 were placed in the chambersof a dual-barrel mixing cartridge and mixed by extruding through astatic mixing-element. The mixed pastes cured in approximately 3 to 3.5minutes (27° C.). The initial color of the C10a/B10 impression paste ispurple and bleaches to a pinkish-red color in approximately 3.5 minutes.The initial color of the C10b/B10 impression paste is green and bleachesto a yellow color in approximately 3.5 minutes.

Example 11

The effect of the hydrosilation inhibitor diethyl maleate (DEM) on thegel time and bleaching time of curable compositions at 25° C. and 85° C.was examined. A stock dye catalyst solution (SDC11) was prepared bytransferring 0.0034 grams of dye #2 and approximately 0.10 grams ofdichloromethane to glass jar. Approximately 50.0 grams of stockcomposition C1 (from Preparatory Example 2) was transferred to the glassjar and mixed with a wooden tongue blade until homogeneous. Similarly, astock dye base solution (SDB11) was prepared by transferring 0.0034grams of dye #2, approximately 0.10 grams of dichloromethane andapproximately 50.0 grams of stock composition B1 (from PreparatoryExample 2) to another glass jar and the components were mixed with awooden tongue-depression blade until homogeneous. Three samplescontaining various amounts of diethyl maleate were prepared bytransferring 0, 1, or 5 μl respectively of diethyl maleate to separate1.5 dram glass vials. Approximately 0.50 grams of the stock solutionSDC11 and 0.50 grams of the stock solution SDB11 were transferred to therespective vials, mixed thoroughly for 30 seconds with a mixing stickand examined for gel time and bleaching time at 25° C.

A second set of similar samples was evaluated for gel and bleaching timeat 85° C. A glass microscope slide was placed on a hot plate heated to85° C. Three samples containing various amounts of diethyl maleate wereprepared by transferring 0, 1, or 5 μl respectively of diethyl maleateto separate 1.5 dram glass vials. Approximately 0.50 grams of the stocksolution SDC11 and 0.50 grams of the stock solution SDB11 weretransferred to the respective vials, mixed thoroughly for 30 secondswith a mixing stick and one drop (˜0.05 grams) of the mixture applied tothe heated glass slide. These samples were probed and visually inspectedboth for gel time and for bleach time. Set out in Table 11a are theamounts of diethyl maleate added and the gel and bleaching times at 25and 85° C.

                  TABLE 11a                                                       ______________________________________                                        Run  DEM     Gel time   Bleach time                                                                           Gel time                                                                             Bleach time                            #    (ml)    (25° C.)                                                                          (25° C.)                                                                       (85° C.)                                                                      (85° C.)                        ______________________________________                                        1    0       135     sec. 210  sec.  8 sec.                                                                              12 sec.                            2    1       1.5     hrs. 8    hrs. 22 sec.                                                                              20 sec.                            3    5       >>48    hrs  Significant                                                                           81 sec.                                                                              15 sec.                                                        bleaching                                                                     at 48 hrs.                                          ______________________________________                                    

The data show that the addition of DEM to hydrosilation-curablecompositions results in room-temperature-stable compositions that can becured and cure-monitored at elevated temperatures. Increasing levels ofDEM result in bleaching times that occur at shorter times relative togel times at 85° C. thus providing potential indicators for workingtime, gel time and setting time.

Example 12

The effect of two additional active-hydrogen (proton) sources on the geltime and bleaching time of curable compositions at room temperature wasevaluated. Four samples containing various amounts of dodecanol ("DDL")were prepared by transferring 0, 5, 10 or 20 μl respectively of DDL toseparate 1.5 dram glass vials. Approximately 0.50 grams of the stocksolution SDC1 and 0.50 grams of the stock solution SDB1 were transferredto the respective vials, mixed thoroughly for 30 seconds with a mixingstick and examined for gel time and bleach time at 25° C.

A second set of samples containing various amounts of acetic acid ("AA")were evaluated for gel and bleaching time at 25° C. Four samplescontaining various amounts of acetic acid were prepared by transferring0, 1, 5 or 10 μl respectively of AA to separate 1.5 dram glass vials.Approximately 0.50 grams of the stock solution SDC1 and 0.50 grams ofthe stock solution SDB1 were transferred to the respective vials, mixedthoroughly for 30 seconds with a mixing stick and examined for gel timeand bleach time at 25° C.

Results for both experiments are shown in Table 12a.

                  TABLE 12a                                                       ______________________________________                                              Indicator                                                               Run # adjuvent (μl)                                                                              Gel time (25° C.)                                                                 Bleach time (25° C.)                  ______________________________________                                        1     DDL      0      158 sec.   244 sec.                                     2     DDL      5      160 sec.   244 sec.                                     3     DDL      10     167 sec.   250 sec.                                     4     DDL      20     190 sec.   310 sec.                                     5     AA       0      150 sec.   220 sec.                                     6     AA       1      154 sec.   150 sec.                                     7     AA       5      240 sec.   140 sec.                                     8     AA       10     600 sec.   ˜150 sec.                                                               (slight blue tinge)                          ______________________________________                                    

The data show that the addition of DDL to hydrosilation-curablecompositions results in minimal change to gel and bleach times. Incontrast, the addition of AA results in longer gel times and shorterbleach times, respectively, at room temperature. Thus the addition ofadjuvents to compositions of the present invention can be utilized toadjust the relationship between the color change and the cure reaction.

Example 13

Indication of cure inhibition is demonstrated in the following examplesutilizing the cure-indicating dental impression materials previouslyexemplified in Examples 9 and 10. A commercially available "acrylate"type adhesive (Scotchbond Multipurpose Dental Adhesive "SBMP" availablefrom 3M, St. Paul, Minn.) was applied to approximately a 5 mm×5 mmsection of a glass microscope slide. Acrylate adhesives sometimes areobserved to retard or inhibit the setting of dental impression materialsthat cure via a hydrosilation mechanism. A purple impression paste fromExample 10 (C10a/B10) was extruded through a static mixer and appliedover much of the slide including the section coated with the SBMP. Thebulk of the impression material exhibited a color change from purple tored/pink in approximately 3.5 minutes. Notably, however, the areapreviously coated with SBMP maintained a purplish coloring (indicatingthat this area was not fully cured). Similar results were obtained forcompositions C10b/B10 (from Example 10) and Run 2 of Example 9.

A two-part (blue catalyst and white base) cure-indicating impressionputty similar to that described in Example 17 was evaluated under twosets of mixing conditions. Approximately 5 grams each of catalyst andbase putties were mixed by hand, wearing vinyl gloves, until ahomogeneous blue paste was obtained. The paste was rolled into a balland allowed to set. A second comparable mix of the catalyst and basecompositions was prepared using latex gloves. Latex gloves sometimes areknown to retard or inhibit the setting of dental impression materialsthat cure via a hydrosilation mechanism. This ball of material also wasallowed to set.

Both balls cured in bulk. The sample mixed with vinyl gloves bleached toa white homogeneous sample. However, the sample mixed with latex glovesexhibited blue and white striations. The striations are believed to beindicative of incomplete curing due to contamination by the latexgloves.

Example 14

A stock impression base paste (B14) was formulated by mixing together150 parts vinyl terminated polydimethylsiloxane having a viscosity of2.0 Pa s ("LMWP"), 4.1 parts organohydrosiloxane crosslinker (PS 122.5,available from United Chemical Technology, Inc., Bristol, Pa.), and 30parts Imsil A-25 filler.

A stock solution of dye M was prepared by dissolving 0.05 parts dye in0.87 parts toluene. A stock solution of dye #2 (DS14) was prepared bydissolving 0.05 parts dye #2 in 1.74 parts of toluene. Additionally, astock paste of dye #2 (DP14) was prepared by dispersing 5 parts dye and5 parts Aerosil R976 fumed silica (available from Degussa Corp., Dublin,Ohio) in 90 parts vinyldimethyl-terminated polydimethyl siloxane with aviscosity of 1.0 Pa s ("VLMWP" available from OSi Specialties Inc.,Danbury, Conn.) using a three-roll mill. A stock solution ofchloroplatinic acid (H₂ PtCl₆ ×6H₂ O, "CPA") catalyst was prepared bydissolving 0.04 parts CPA in 0.79 parts isopropanol.

Cure-indicating formulations were prepared by adding sufficient amountsof dye and catalyst to 30.7 parts of base paste (B14) to give 100 ppmdye (based on LMWP) and 30 ppm Pt (based on LMWP), and mixing by hand.Formulations were monitored for gel point, cure point, and bleach pointas shown in Table 14a.

                  TABLE 14a                                                       ______________________________________                                        Run    Dye    Gel Point  Cure Point                                                                             Bleach Point                                ______________________________________                                        1      M      70-80 min. 180-240 min.                                                                           DNB.sup.1                                   2      #2.sup.2                                                                             >300 min.  <1200 min.                                                                             PB.sup.3                                    3      #2.sup.4                                                                             >300 min.  <1200 min.                                                                             PB                                          ______________________________________                                         .sup.1 "DNB" = did not bleach after 72 hours.                                 .sup.2 As a toluene solution (DS14).                                          .sup.3 "PB" = partial bleaching occurred.                                     .sup.4 As a dispersed paste (DP14).                                      

Notably, comparison dye M did not exhibit bleaching over the 72 hourperiod after the curing reaction was begun, while dye #2 exhibited somepartial bleaching in this non-preferred composition.

Example 15

The above experiment was repeated with the following changes: 1) the dyeconcentration was increased to 200 ppm based on LMWP; 2) a CPA stocksolution was prepared by dissolving 0.10 parts CPA in 0.79 partsisopropanol; and 3) 0.15 parts Silwet L-77 surfactant per 15.3 partsimpression paste was added to the indicated run numbers. Formulationswere monitored for gel point, cure point, and bleach point as shown inTable 15a.

                  TABLE 15a                                                       ______________________________________                                        Run  Silwet  Dye     Gel Point                                                                              Cure Point                                                                            Bleach Point                            ______________________________________                                        1    No      M        120 min.                                                                              <1320 min.                                                                            .sup. DNB.sup.1                         2    Yes     M       >420 min.                                                                              <1320 min.                                                                            DNB                                     3    No      #2.sup.2                                                                              >1440 min.                                                                             <2880 min.                                                                            DNB                                     4    Yes     #2.sup.2                                                                               230 min.                                                                              <1320 min.                                                                            230 min.                                ______________________________________                                         .sup.1 DNB  did not bleach after 72 hours.                                    .sup.2 As a toluene solution (DS14).                                     

The composition containing Silwet and Dye #2 (Run 4) exhibitedbleaching, while the composition containing Silwet and comparison dye M(Run 2) did not bleach.

Example 16

A stock catalyst solution (C16A) was prepared by combining 400 parts ofvinyldimethyl-terminated poly(dimethylsiloxane) with a viscosity of 2.0Pa s ("LMWP") with 11 parts of Pt catalyst (from Preparatory Example1a). A stock catalyst solution (C16S) was prepared by combining 400parts of vinyldimethyl-terminated poly(dimethylsiloxane) with aviscosity of 2.0 Pa s ("LMWP") with 11 parts of Pt catalyst (fromPreparatory Example 1a) and 8 parts Silwet L-77 surfactant. A stock basesolution (B16) was prepared by combining 12.5 partsorganohydropolysiloxane crosslinker ("XL1") with 0.25 parts1,1,3,3-tetramethyl-1,3-divinyldisiloxane inhibitor ("DVTMDS"). 0.04parts DP14 was added to 20 parts of catalyst solutions C16A or C16S.Synthetic or mineral fillers were added according to Table 16a toprepare impression material pastes. These pastes were cured by adding2.55 parts of base stock solution B16 and mixing for 120 seconds. Theinitial color, gel time, cure time, and bleach time for each run arelisted in Table 16a.

                  TABLE 16a                                                       ______________________________________                                             Filler.sup.2,                                                            Run.sup.1                                                                          parts     Color   Gel Time                                                                             Cure Time                                                                             Bleach Time                             ______________________________________                                        1A   none      Blue    6.5 min.                                                                             9 min.  9 min.                                  1S   none      Blue    6.5 min.                                                                             9 min.  9 min.                                  2A   Imsil, 4  Blue-   6.5 min.                                                                             9 min.  >20 min.                                               grey                                                           2S   Imsil, 4  Blue    6.5 min.                                                                             9 min.  9 min.                                  3A   Vicron, 4 Blue    6.0 min                                                                              9 min.  9 min.                                  3S   Vicron, 4 Blue    6.0 min.                                                                             9 min.  9 min.                                  4A   Talc, 4   Blue-   6.0 min.                                                                             9 min.  >15 min.                                               grey                                                           4S   Talc, 4   Blue    6.0 min.                                                                             9 min.  12 min.                                 5A   Alumina, 4                                                                              Blue    5.0 min.                                                                             8 min.  8 min.                                  5S   Alumina, 4                                                                              Blue    6.0 min.                                                                             9 min.  9 min.                                  6A   Quso, 2   Blue    5.0 min.                                                                             7 min.  7 min.                                  6S   Quso, 2   Blue    5.0 min.                                                                             7.5 min.                                                                              7.5 min.                                7A   Aerosil   Blue-   5.0 min.                                                                             7 min.  >20 min.                                     R976, 1   green                                                          7S   Aerosil   Blue    5.0 min.                                                                             7 min.  7 min.                                       R976, 1                                                                  8A   Cabosil   Green   4.0 min.                                                                             6 min.  >20 min.                                     M5, 1                                                                    8S   Cabosil   Blue    4.5 min.                                                                             6.5 min.                                                                              6.5 min.                                     M5, 1                                                                    ______________________________________                                         Footnotes for Table 16a:                                                      .sup.1 Run numbers with an "A" contain stock catalyst solution C16A wile      run numbers with an "S" contain stock catalyst solution C16S.                 .sup.2 "Quso" = Quso WR55. "Cabosil M5" = hydrophilic fumed silica            available from Cabot Corp., Tuscola, Il. "Imsil" = Imsil A25. "Vicron" =      Vicron 453 calcium carbonate available from Pfizer, Inc., New York, NY.       "Talc" = Beaverwhite 200 hydrous magnesium silicate available from Cyprus     Industrial Minerals, Inc., Englewood, CO. "Alumina" = A208 hydrated           aluminum oxide available from R. J. Marshall, Inc., Southfield, MI.      

Notably, the inclusion of certain fillers appears to affect both theinitial paste color and the bleach time. For fillers which affect colorand bleach time, the effect can be reversed with Silwet L-77.

Example 17

Cure-indicating putty catalyst and base impression materials wereprepared by mixing the following ingredients in a 1 gallon Ross mixer:

                  TABLE 17a                                                       ______________________________________                                        Ingredient    Catalyst (parts)                                                                          Base (parts)                                        ______________________________________                                        LMWP          5.80        5.00                                                HMWP.sup.1    13.60       11.70                                               Pt Catalyst.sup.2                                                                           0.60        --                                                  Crosslinker.sup.3                                                                           --          3.10                                                Mineral Oil.sup.4                                                                           6.50        6.50                                                Vicron 45-3   36.75       36.75                                               Imsil A-25    36.75       36.75                                               Silwet L-77   --          0.35                                                DVTMDS        --          0.0067                                              Dye #2        --          0.006                                               ______________________________________                                         Footnotes for Table 17a:                                                      .sup.1 "HMWP" = vinylterminated poly(dimethylsiloxane) with a viscosity o     60 Pa s and molecular weight approximately 60,000 g/mol.                      .sup.2 From Preparatory Example 1a.                                           .sup.3 "Crosslinker" = A methylhydrosiloxanedimethylsiloxane copolymer        with a viscosity between about 50 and 70 mPa · s and having          approximately 0.13% active hydrogen ("XL2").                                  .sup.4 "Mineral Oil" = Kaydol ™ white mineral oil, USP grade available     from Witco Chemical Corp., Conneborn Div., Chicago, IL.                  

Catalyst and base putty impression material pastes were mixed togetherto give a cure-indicating formulation with T5=127 sec.; T90=190 sec.;and Bleach time=292 sec. at 27° C.

Example 18

Preparation of a Silwet-free impression material. Impression materialcatalyst and base pastes were prepared by mixing the followingingredients:

                  TABLE 18a                                                       ______________________________________                                        Ingredient    Catalyst, Parts                                                                           Base, Parts                                         ______________________________________                                        VLMWP         83.1        51.2                                                Pt Catalyst.sup.1                                                                           3.04        --                                                  Crosslinker.sup.2                                                                           --          34.12                                               DVTMDS        --          0.07                                                Vicron 45-3   107.5       108.5                                               Quso WR-55    6.1         7.1                                                 Dye #2        0.014       --                                                  ______________________________________                                         Footnotes for Table 18a:                                                      .sup.1 From Preparatory Example 1a.                                           .sup.2 "XL2".                                                            

Catalyst and base pastes were placed in separate barrels of adual-barrel syringe and extruded through a static-mixing element. Thematerial had a T5=129 sec.; T90=160 sec.; and Bleach time=240 sec. @ 27°C.

Example 19

Preparation of size-reduced structural abrasive molds. Stock catalystand base solutions were prepared for use in fabricating size-reducedmolds by mixing the following:

                  TABLE 19a                                                       ______________________________________                                        Ingredient    Catalyst (parts)                                                                          Base (parts)                                        ______________________________________                                        LMWP          1325        1010                                                HMWP           667         667                                                Pt Catalyst.sup.1                                                                             8         --                                                  Crosslinker.sup.2                                                                           --           320                                                DVTMDS        --            3                                                 VMP Naphtha   2000        2000                                                ______________________________________                                         Footnotes for Table 19a:                                                      .sup.1 From Preparatory Example 1a                                            .sup.2 "XL2"-                                                            

Catalyst and base solutions were mixed and poured against a flat,structured die. The system was closed to prevent solvent evaporation.After three hours the material cured and a color change from blue toclear occurred over a period of about 15 min. At this point the curedsample was removed from the die and solvent was allowed to evaporate toform a size-reduced mold 50% of the original die volume.

Example 20

A stock catalyst resin solution (C20) was prepared by mixing 190 partsVLMWP, 4.72 parts platinum catalyst from Preparatory Example 1a, and3.30 parts Silwet L-77. A stock base resin solution (B20) was preparedby mixing 193 parts VLMWP, 0.21 parts divinyltetramethyl disiloxane,98.82 parts XL2, and 4.95 parts Silwet L-77. A stock dye paste (DP20)was prepared from 83 parts VLMWP, 12 parts Quso WR-55 and 5 parts dye #2using a three-roll mill. Impression material catalyst pastes wereprepared by mixing 90 parts C20, 10 parts Quso WR-55, 100 parts ImsilA-25 and optionally 0.30 parts DP20. Impression material base pasteswere prepared by mixing 90 parts B20, 10 parts Quso WR-55, 100 partsImsil A-25 and optionally 1.4 parts of pink or yellow fluorescentpigment (Aurora Pink AX-11 or Saturn Yellow AX-17, available fromDAY-GLO Color Corp., Cleveland, Ohio). Curing impression pastes wereprepared by placing catalyst and base pastes into separate barrels of adual barrel syringe and extruding through a static mixer.

Initial and final colors were determined using a colorcomputer/spectrophotometer instrument (a Milton Roy Diano Match Scan IIdouble beam spectrophotometer with a diffuse lighting source).Measurements were taken using a sample area view of 25 mm diameter andwith specular reflection included. The surface colors of 3 mm thickslabs of impression pastes were measured and reported in the CIE L*A*B*color system (as described in "Principles of Color Technology",Billmeyer & Saltzman, Second Edition, 1981). This system is based on a3-dimensional color space with the positive X-axis representing red, thenegative X-axis representing green, the positive Y-axis representingyellow, the negative Y-axis representing blue, and the Z-axis going fromzero (black) to 100 (white) with the origin at 50.

                  TABLE 20a                                                       ______________________________________                                                                         Final Color of                                                      Initial Color of                                                                        Composition after                            Run # Dye     Pigment  Composition                                                                             curing                                       ______________________________________                                        1     None    None     Off White Off White                                    2     +       None     Blue      Off White                                    3     None    Pink     Pink      Pink                                         4     +       Pink     Purple    Pink                                         5     None    Yellow   Yellow    Yellow                                       6     +       Yellow   Green     Yellow                                       ______________________________________                                    

                                      TABLE 20b                                   __________________________________________________________________________                             Final Color                                                                   Difference (ΔE*).sup.1                                                  between sample                                                                         Color difference                                Initial L*A*B*       having dye and                                                                         (ΔE*) between                             Color (immed. after                                                                     Final L*A*B* Color                                                                       control sample                                                                         initial and final                           Run #                                                                             mixing)   (after curing)                                                                           having no dye                                                                          color                                       __________________________________________________________________________    1   70.00/2.01/6.68                                                                         70.04/1.91/6.88                                                                          0.71      0.23                                       2   63.03/-6.52/-4.67                                                                       69.94/1.36/6.44     15.27                                       3   63.14/26.50/-0.65                                                                       63.11/26.31/-0.51                                                                        2.93      0.24                                       4   57.82/9.93/-9.80                                                                        62.80/23.63/-1.66   16.70                                       5   71.66/-3.71/20.73                                                                       71.70/-3.66/20.68                                                                        1.97      0.08                                       6   63.02/-13.17/8.13                                                                       70.17/-4.36/19.65   16.17                                       __________________________________________________________________________     Footnotes for Tables 20a and 20b:                                             .sup.1 "ΔE*" = [(L.sub.1 * - L.sub.2 *).sup.2 + (A.sub.1 * - A.sub.     *).sup.2 + (B.sub.1 * - B.sub.2 *).sup.2 ].sup.1/2 where L.sub.1 *A.sub.1     *B.sub.1 * and L.sub.2 *A.sub.2 *B.sub.2 * are the colors of the samples      being compared. As a general rule, colors which differ by less than about     3 ΔE* units cannot be distinguished readily by the human eye.      

This experiment illustrates that complete bleaching of the dye occurs asthe compositions react and cure. This is illustrated by comparison ofthe final colors of the samples with dye #2 and without dye #2. Forexample, the difference between the final (i.e., post cure) colors ofRun #1 and Run #2 is about 0.71 ΔE* units. This minor difference incolor would be well below that level which could be detected by thehuman eye. Similarly, comparing Runs 3 and 4 and Runs 5 and 6 yields ΔE*values below the level which is detectable easily by the human eye.

This experiment also illustrates that readily-observable color changesoccur in the samples containing cure indicating dye. Runs 1, 3 and 5 donot contain any cure-indicating dye and do not change color as a resultof the curing process (ΔE* values for these runs are 0.23, 0.24, and0.08, respectively). Runs 2, 4 and 6 each contain a cure-indicating dye.Notably, these runs also exhibit large color changes (15.27, 16.70, and16.17, respectively) as the samples are cured. For dental impressionmaterials (and similar compositions which are monitored by the humaneye) the amount of color change exhibited by the dye need only be thatamount of change that can be observed by the human eye. Preferably, theimpression material exhibits a color change upon curing of at least 5ΔE*units when tested as described above. More preferably, the impressionmaterial exhibits a color change upon curing of at least 10 ΔE* units.Most preferably, the impression material exhibits a color change uponcuring of at least 15ΔE* units.

DESCRIPTION OF DRAWING

FIG. 1 illustrates ΔE* as a function of curing time graphically for runs2, 4, and 6. To generate these plots the samples were mixed and placedin the spectrophotometer. An initial color scan was obtained (withinless than 1.25 minutes) and used as the reference color. Additionalscans were taken as the material cured and were compared to the initialscan. The difference in color (ΔE*) was computed for each additionalscan and plotted. Table 20c contains the raw data for these scans. Ascan be seen in FIG. 1 the color change was very pronounced for thesesamples (initial color→final color) and occurred over a very short timeperiod. Notably, the color change for each sample coincided with the gelpoint of the material. Thus, the pronounced, rapid color change was avery good indicator of the set time of the material. T90 for Runs 2, 4,and 6 was 5.28, 5.37 and 5.20 minutes, respectively, the time at whichthe color has changed to within 3 ΔE* units of the final color.Additionally, the time at which the initial color changes 3 ΔE* traitsfrom the initial color corresponds approximately with the T5 for Runs 2,4, and 6 of 3.8, 3.9, and 3.9 minutes, respectively. This demonstratesthe effectiveness of indicating both the working time and setting timein a single formulation.

                  TABLE 20c                                                       ______________________________________                                        Time (Minutes)                                                                           Run 2 (ΔE*)                                                                        Run 4 (ΔE*)                                                                        Run 6 (ΔE*)                            ______________________________________                                        1.25       0.13       0.09       0.14                                         1.50       0.24       0.19       0.27                                         1.75       0.37       0.30       0.41                                         2.00       0.50       0.42       0.55                                         2.25       0.64       0.55       0.71                                         2.50       0.79       0.69       0.86                                         2.75       0.94       0.85       1.05                                         3.00       1.12       1.03       1.23                                         3.25       1.32       1.22       1.45                                         3.50       1.57       1.48       1.71                                         3.75       1.86       1.79       2.02                                         4.00       2.25       2.21       2.41                                         4.25       2.85       2.87       2.96                                         4.50       3.83       4.12       3.79                                         4.75       6.83       8.48       5.59                                         5.00       11.37      13.03      10.81                                        5.25       13.76      14.86      14.15                                        5.50       14.62      15.59      15.36                                        5.75       14.95      16.00      15.77                                        6.00       15.12      16.25      15.95                                        6.25       15.21      16.45      16.05                                        6.50       15.26      16.59      16.12                                        6.75       15.32      16.70      16.18                                        ______________________________________                                    

Example 21

A stock catalyst resin solution (C21) was prepared by mixing 2928 pansLMWP with 72 parts of the catalyst from Preparatory Example 1a.Cure-indicating catalyst pastes were prepared by mixing 295 parts C21,4.5 parts of surfactant or wetting agent according to Table 21, 30 partsQuso WR-55, 300 parts Imsil A-25, and 0.96 parts stock solution DP20 ina double planetary Ross mixer. A base impression paste (B21) wasprepared by mixing 465 parts VLMWP, 195 parts XL2, 1.0 parts DVTMDS, 60parts Aerosil R976, and 780 parts Imsil A-25 in a double planetary Rossmixer. The catalyst and base impression pastes were placed in separatebarrels of a dual barrel syringe, extruded through a static-mixing tipand checked visually for color change upon curing. Results are given inTable 21.

                  TABLE 21                                                        ______________________________________                                        Run    Wetting Agent Initial Color.sup.1                                                                       Cured Color                                  ______________________________________                                        1      none          Grey        Grey                                         2      Neodol ® 1-9.sup.2                                                                      Blue        Off White                                    3      Carbowax ®.sup.3                                                                        Blue        Off White                                    4      Triton X102.sup.4                                                                           Blue        Off White                                    5      Fluorad FC170C.sup.5                                                                        Blue        Off White                                    6      Fluorad FC430.sup.5                                                                         Blue        Off White                                    7      Dibasic ester.sup.6                                                                         Blue        Off White                                    ______________________________________                                         .sup.1 "Initial Color" is the color of the catalyst impression paste.         .sup.2 Available from Shell Chemical Co., Houston, TX.                        .sup.3 Sentry ® polyethylene glycol 400, available from Union Carbide     Chemicals and Plastics Co., Inc., Danbury, CT.                                .sup.4 Available from Rohm and Haas Co., Philadelphia, PA.                    .sup.5 Available from 3M Co., St. Paul, MN.                                   .sup.6 A mixture of dimethyl glutarate, dimethyl adipate, and dimethyl        succinate and available from E. I. duPont deNemours, Wilmington, DE. This     impression material paste was prepared using a Semkit 388 mixer as            previously described.                                                    

The above example illustrates that a variety of surfactants or wettingagents can be employed in filled compositions of the present invention.The filled composition of Run #1 did not exhibit an initial "blue" coloras did Runs 2-7 which contained a wetting agent. The compositions with awetting agent all exhibited a readily observable color change uponcuring.

Example 22 Reduction Potential and Spectroscopic Data of Various Dyes

Reduction potentials by Cyclic Voltammetry: For a discussion of theunderlying theory of potentiometry in organic solvents, the preferredmethod of referencing voltage measurements by means of ferricenium andcobalticenium salts, and the use of Cyclic Voltammetry for making suchmeasurements, we incorporate herein by reference "The Chemistry ofNonaqueous Solvents", Volumes I (1966) and IV (1976), edited by J. J.Lagowski, Academic Press, New York, and specifically the chapter inVolume I entitled "Electrode Potentials in Non-Aqueous Solvents" by H.Strehlow, notably page 159, and the chapter in Volume IV entitled "RedoxSystems in Nonaqueous Solvents" by M. Rumeau, notably pages 90 and 96.

Based on the foregoing, solutions were made having approximately 0.0100molar dye in a 0.100 molar solution of tetrabutylammoniumtetrafluoroborate in dry 99% acetonitrile--1% trifluoroethanol (byvolume). The reduction potentials were measured with respect to thesaturated calomel electrode at a scan rate of 20 V per second towardmore negative values, and are reported as the peak potential.

Conversion to other electrode/potential scales may be carried out bymaking use of the values measured for the reduction potentials ofcobalticenium and ferricenium salts, as reported in Table 22. Thisprocedure also is applicable when correcting for reasonablemodifications in the solvent system necessitated by experimental factorssuch as solubility. Reduction potentials thus obtained are reported inTable 22. Preferred cure-indicating dyes, for use in the presentinvention, have a reduction potential greater than -0.80. More preferredcure-indicating dyes have a reduction potential between 0 and -0.80.

Spectroscopic measurements: The dye solutions prepared for Cyclicvoltammetry were diluted to 0.000050 molar in dry spectro-gradeacetonitrile, and their spectra were measured from 200 to 800 nm in 10mm silica cells, by means of a Perkin-Elmer No. 330 spectrophotometer.In the event that the maximal absorbance exceeded 3.0, a furtherfivefold dilution to 0.000010 molar was performed. In Table 22 is listedthe wavelengths of maximal absorption (λ_(max)) in nanometers (nm) andthe wavelengths (short and long, respectively) at which the absorbancehad fallen to one-half its maximal value. The latter serve to indicatethe peak breadth and shape. The "Molar Extinction Coefficient", alsotermed "Molar Absorbance", (ε), is the measured absorbance corrected forconcentration of the dye. In cases of commercial dyes for which thestructures have not been disclosed, a nominal molecular weight of 475was used to calculate molarities. In some cases, notably Sample No. 55,lack of purity means that the true molar extinction coefficients will beproportionately larger than the reported values. As is conventional inspectrophotometry, the common logarithms of the molar extinctioncoefficients is also reported in Table 22.

                                      TABLE 22                                    __________________________________________________________________________               Wave-                                                                         length of    Wavelengths of                                                   Maximal                                                                              Molar Half-maximal                                               C.V.  Visible                                                                              extinction                                                                          Visible Absorption                                    Sample                                                                             Reduction                                                                           Absorption                                                                           Coefficient                                                                         (nm)                                                  No.  Potential                                                                           (nm)λ.sub.max                                                                 ε                                                                           λ'.sub. 1/2                                                                 λ".sub. 1/2                                                                 Log ε                               __________________________________________________________________________     2   -0.73 645    31,300                                                                              587  703  4.50                                         5   -1.01 607    14,700                                                                              536  667  4.17                                         6   -0.98 602    15,200                                                                              535  663  4.18                                        11   -0.97 532    9,200 464  593  3.97                                        14   -0.5  675    26,600                                                                              617  731  4.42                                        15   -0.55 687    32,000                                                                              630  740  4.51                                        16   -0.95 612    16,800                                                                              544  673  4.23                                        17   -0.87 660    3,800 591  724  3.57                                        19   -0.96 476    2,400 --   580  3.37                                        21   -0.29 525    1,700 --   641  3.22                                        23   -0.9  547    1,800 --   621  3.26                                        34   -0.99 374    3,600 338  418  3.56                                        43   -0.24 488    15,200                                                                              437  525  4.18                                        46   -0.86 479    27,000                                                                              438  512  4.43                                        48   -0.61 498    26,700                                                                              459  533  4.43                                        51   -1.26 588    178,200                                                                             570  605  5.25                                        52   -0.49 638    113,900                                                                             593  667  5.06                                        53   -0.78 532    125,800                                                                             498  552  5.10                                        54   -0.67 560    54,800                                                                              509  586  4.74                                        55   --    661    >5,000                                                                              600  703  >3.7                                        56   -0.71 542    114,200                                                                             508  562  5.06                                        58   -0.61 627    73,700                                                                              583  655  4.87                                        59   -0.63 543    68,900                                                                              509  566  4.84                                        60   -0.97 527    112,200                                                                             472  576  5.05                                        61   --    546    1,900 --   621  3.27                                        77   -0.50 639    176,000                                                                             609  663  5.25                                        A    -1.20 391    16,100                                                                              331  443  4.21                                        B    -1.04 472    13,800                                                                              375  515  4.14                                        D    -1.09 483    15,600                                                                              383  530  4.19                                        E    -0.93,                                                                              514    15,300                                                                              432  562  4.19                                             -1.35                                                                    F    -0.89,                                                                              501    21,100                                                                              434  545  4.33                                             -1.4                                                                     G    -0.88,                                                                              508    25,300                                                                              449  553  4.40                                             -1.23                                                                    I    -1.15 593,   11,900,                                                                             555  658  4.08,                                                  600    13,900          4.14                                        K    -1.19 590,   15,800,                                                                             555  653  4.20,                                                  636    18,600          4.27                                        L    -0.82 581    7,000 509  635  3.85                                        Cobalt-                                                                            -0.939                                                                   icenium                                                                       Hexa-                                                                         fluoro-                                                                       phosphate                                                                     (Ref)                                                                         Ferri-                                                                             +0.453                                                                   cenium                                                                        Hexa-                                                                         fluoro-                                                                       phosphate                                                                     (Ref)                                                                         __________________________________________________________________________

Example 23

A stock catalyst paste was prepared by combining in a Ross mixer 33parts platinum catalyst (Preparatory Example 1a), 1449 partsvinyl-terminated polydimethylsiloxane having a viscosity of 2.0 Pa.s"LMWP"), and 180 parts Quso WR-55 and mixing 10 minutes at 30 rpm. 1320parts of Imsil A-25 was added and mixed 70 minutes at 30 rpm undervacuum. 18 parts of Silwet L-77 was added and mixed 35 minutes at 30 rpmunder vacuum to make catalyst paste C23.

Base pastes were prepared by adding the indicated number of parts of dyeto 3.3 parts Silwet L-77, see Table 23. The Silwet/dye mixture was addedto a mixture of 136 parts LMWP, 54 parts of organohydrogenpolysiloxane,XL2, and 0.17 parts 1.3-divinyl-1,1,3,3-tetramethyldisiloxne and shakenvigorously. 180 parts of this mixture and 22.5 parts of Quso WR-55 wereadded to a Ross mixer and mixed for 10 minutes at 40 rpm. 173 parts ofImsil A-25 was added and mixed 70 minutes at 40 rpm under vacuum to formblue base pastes B23. These catalyst and base pastes were placed inseparate barrels of a dual barrel syringe and evaluated for bleachingand curing properties.

                  TABLE 23                                                        ______________________________________                                        Run  Dye          Dye, parts                                                                              Cure Indicator Result                             ______________________________________                                        1    CMDI-TMHE    0.042     bleaches at cure point                            2    CMDDI        0.038     bleaches at cure point                            3    CMDI-CI      0.090     bleaches at cure point                            4    CDHI         0.080     bleaches at cure point                            5    CMDI-OH      0.024     not soluble in formulation                        6    CDI          0.022     bleaches at cure point                            7    CMDI-TMSether                                                                              0.043     bleaches at cure point                            8    TC-Bu2       0.040     bleaches before cure point                        9    TC-Et3       0.040     bleaches before cure point                        10   S,N-compound 0.040     not soluble in formulation                        11   CMDI-PIV*    0.040     bleaches at cure point                            ______________________________________                                         *Silbond ® 3000MST-M filler (available from Quarzwerke GmbH, Freschen     Germany) was substituted for Imsil in the base paste for run #11.        

Compounds 1 and 3-11 were tested according to the procedure of Example4. They bleached according to the description defined in Example 4.

The chemical structures of these dyes are as follows:

CMDI-TMHE Example 23 #12-Chloro-4-[[2-methyl-4-(N-ethyl-N-(2-(3,5,5-trimethylhexanoxy)ethyl)amino)phenyl]imino]-2,5-cyclohexadien-1-one##STR29## CMDI-TMSether Example 23 #72-Chloro-4-[[2-methyl-4-(N-ethyl-N-(3,5-dioxa-7-(trimethylsilyl)heptyl)amino)phenyl]imino]-2,5-cyclohexandien-1-one##STR30## CMDDI Example 23 #22-Chloro-4-[[4-(N-dodecyl-N-methylamino)phenyl]imino]-2,5-cyclohexandien-1-one##STR31## CDHI Example 23 #42-Chloro-4-[[4-(dihexylamino)phenyl]imino]-2,5-cyclohexadien-1-one##STR32## CMDI-PIV Example 23 #112-Chloro-4-[[2-methyl-4-(N-ethyl-N-(2-dimethylproprionoxy)ethyl)amino)phenyl]imino]-2,5-cyclohexadien-1-one##STR33## CMDI-OH Example 23 #52-Chloro-4-[[2-methyl-4-(N-ethyl-N-(2-hydroxyethyl)amino)phenyl]imino]-2,5-cyclohexadien-1-one##STR34## CMDI-Cl Example 23 #32-Chloro-4-[[2-methyl-4-(N-ethyl-N-(2-chloroethyl)amino)phenyl]imino]-2,5-cyclohexadien-1-one##STR35## CDI Example 23 #62-Chloro-4-[[4-diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one##STR36## Example 24 Preparation of 2-Phenyl-1,1,3-tricyanopropylene

A mixture of 250 grams (1.722 mol, 1 eq) of benzoylacetonitrile, 284grams (270 mL, 4.306 mol, 2.5 eq) of malononitrile and 138 grams (1.784mol, 1.04 eq) of ammonium acetate in 2500 mL of ethanol was heated toreflux for 1.5 hours and then cooled to room temperature. To thismixture was added 190 mL of 12M hydrochloric acid dropwise with cooling(ice/water bath). The mixture was placed in a separate flask and a solidformed. To this mixture was added 3300 mL of water with stirring. Thesolid was collected and washed with 2 liters of water and stirred with1200 mL of ethanol to give 203.3 grams (61% yield) of product.

Example 25 Preparation of3-[[4-(diethylamino)phenyl]imino]-2-phenyl-1-propene-1,1,3-tricarbonitrile

A solution of 15.0 grams (0.0776 mol 1 eq) of2-Phenyl-1,1,3-tricyanopropylene in 75 mL of ethanol was prepared byheating to approximately 65° C. To this was added, dropwise, a solutionof 13.8 grams (0.0776 mol 1 eq) of N,N-diethyl-4-nitrosoaniline in 450mL of ethanol at such a rate that the temperature did not go below 60°C. and then the mixture was stirred at 60° C. for 30 minutes. After theaddition, the reaction was cooled to room temperature overnight and theprecipitate was collected, washed with ethanol and air dried to give5.74 grams (21% yield) of product, mp 212°-215° C. (dec).

The above procedure was used for the preparation of3-[[4-dibutylamino)phenyl]imino]-2-phenyl-1-propene-1,1,3-tricarbonitrileusing N,N-dibutyl-4-nitrosoaniline in place ofN,N-diethyl-4-nitrosoaniline.

Example 264[(3-methyl-2(3H)-benzothiazolyidene)methyl]-1,2-naphthoquinone

A solution of 4.35 grams (0.0776 mol, 4.91 eq) of potassium hydroxidewas dissolved in 30 mL of water and added to a solution of 4.35 grams(0.0158 mol, 1 eq) of 2,3-dimethylbenzothiazolium methyl sulfate in 30mL of water. The reaction mixture was stirred with 50 mL of benzene for15 minutes. This mixture was added to a mixture of 5.0 grams (0.03 16mol, 2 eq) of 1,2-naphthoquinone in 50 mL of benzene and the resultingmixture was stirred for 1.5 hours at room temperature. The solid wascollected by filtration and washed with water, hot ethanol and ether.

The solid was washed with refluxing ethanol and filtered hot to remove ayellow solid. The solid was washed with 50 mL of hot benzene andfiltered hot. The residue was collected and air dried to give theproduct.

Compounds of examples 23, runs 2, 4, 5, and 6 were prepared according tothe procedure for Preparatory Example 3, using the appropriatelysubstituted phenylene diamine starting material. Additional compoundsmay be synthesized using techniques and starting materials that will bereadily apparent to the ordinary synthetic chemist. For example, furthersubstituents may be provided by reaction with the hydroxyl functionalityof Example 23, run 5.

Various modifications and alterations of this invention will be apparentto those skilled in the art without departing from the scope and spiritof this invention, and it should be understood that this invention isnot limited to the illustrative embodiments set forth herein. ##STR37##

What is claimed is:
 1. A curable composition, comprising: anethylenically unsaturated compound having more than one ethylenicallyunsaturated group;a crosslinker compound containing a multiplicity ofSiH groups; a catalyst capable of catalyzing a hydrosilation reaction;and a cure-indicating dye that exhibits a color change, in a dyeevaluation test, at 25° C. when 500 mg of said dye, about 500 ml ofdichloromethane, 100 ml of pentamethyldisiloxane, and 10 ml of ahydrosilation catalyst solution having between about 2 and 3 weightpercent platinum are mixed together, wherein said dye is represented bythe formula ##STR38## wherein each of R⁴⁸, R⁴⁹, and R⁵⁰, isindependently selected from the group consisting of: hydrogen, halogenand an acyclic, alicyclic or aromatic hydrocarbyl group optionallyinterrupted with one or more heteroatoms, each of R⁵¹, R⁵², R⁵³, R⁵⁴,R⁵⁵, and R⁵⁶ is independently selected from the group consisting ofhydrogen and an acyclic, alicyclic or aromatic hydrocarbyl groupoptionally interrupted with one or more heteroatoms, and optionally, anytwo of R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and R⁵⁶ may together form an alicyclic oraromatic ring.
 2. The composition of claim 1, wherein each of R⁴⁸, R⁴⁹,and R⁵⁰ is independently selected from the group consisting of hydrogenalkyl and halogen; and each R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ isindependently selected from the group consisting of hydrogen and alkylthat is optionally substituted by one or more cyano, alkoxy, hydroxy,alkylsiloxy, alkylsilyl, acyl, aryl, halo, arylsiloxy, arylsilyl, amino,and mono or dialkyl amino groups.
 3. The composition of claim 1, whereinat least one of R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ is selected from thegroup consisting of--CH₂ OSi(CH₃)₂ C(CH₃)₃ --CH₂ OC(O)CH₂ CH(CH₃)CH₂C(CH₃)₃ --CH₂ OC(O)C(CH₃)₃ --CH₂ OCH₂ OCH₂ CH₂ Si(CH₃)₃ --CH₂ Cl --CH₂OC(O)NHCH₂ CH₂ CH₂ CH₃, and --CH₂ OC(O)NHCH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃.
 4. Acurable composition, comprising:an ethylenically unsaturated compoundhaving more than one ethylenically unsaturated group; a crosslinkercompound containing a multiplicity of SiH groups; a catalyst capable ofcatalyzing a hydrosilation reaction; and a cure-indicating dye thatexhibits a color change in a dye evaluation test, at 25° C. when 500 mgof said dye, about 500 ml of dichloromethane, 100 ml ofpentamethyldisiloxane, and 10 ml of a hydrosilation catalyst solutionhaving between about 2 and 3 weight percent platinum are mixed together,wherein said dye is represented by the formula ##STR39## wherein X⁴ isN--R⁶⁷ R⁶⁸, O--R⁶⁹, S--R⁷⁰ or CR⁷¹ R⁷² R⁷³ and wherein each of R⁵⁸, R⁵⁹,R⁶⁰, R⁶¹, R⁶², R⁶³, R⁶⁴, R⁶⁵, R⁶⁶, is independently selected from thegroup consisting of hydrogen, halogen, a hydrocarbyl group optionallyinterrupted with one or more heteroatoms and an acyclic, alicyclic oraromatic heterocyclic group, and each of R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰, R⁷¹, R⁷²,and R⁷³ is independently selected from the group consisting of hydrogen,a hydrocarbyl group optionally interrupted with one or more heteroatomsand an acyclic, alicyclic or aromatic heterocyclic group.
 5. Thecomposition of claim 4, wherein each or R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰, R⁷¹, R⁷²,and R⁷³ is independently selected from the group consisting of hydrogenand alkyl that is optionally substituted by one or more cyano, alkoxy,hydroxy, alkylsiloxy, alkylsilyl, acyl, aryl, halo, arylsiloxy,arylsilyl, amino, and mono or dialkyl amino groups.
 6. The compositionof claim 4, wherein at least one of R⁶⁷, R⁶⁸, R⁶⁹, R⁷⁰, R⁷¹, R⁷², andR⁷³ is selected from the group consisting of--CH₂ CH₂ OSi(CH₃)₂ C(CH₃)₃--CH₂ CH₂ OC(O)CH₂ CH(CH₃)CH₂ C(CH₃)₃ --CH₂ CH₂ OC(O)C(CH₃)₃ --CH₂ CH₂OCH₂ OCH₂ CH₂ Si(CH₃)₃ --CH₂ CH₂ Cl --CH₂ CH₂ OC(O)NHCH₂ CH₂ CH₂ CH₃,and --CH₂ CH₂ OC(O)NHCH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃.
 7. A curablecomposition, comprising:an ethylenically unsaturated compound havingmore than one ethylenically unsaturated group; a crosslinker compoundcontaining a multiplicity of SiH groups; a catalyst capable ofcatalyzing a hydrosilation reaction; and a cure-indicating dye thatexhibits a color change in a dye evaluation test, at 25° C. when 500 mgof said dye, about 500 ml of dichloromethane, 100 ml ofpentamethyldisiloxane, and 10 ml of a hydrosilation catalyst solutionhaving between about 2 and 3 weight percent platinum are mixed together,wherein said dye is selected from compounds of the formula ##STR40## 8.A curable composition, comprising:a compound having more than oneethylenically unsaturated group; a crosslinker compound containing amultiplicity of SiH groups; a catalyst capable of catalyzing ahydrosilation reaction; and a cure-indicating dye that exhibits a colorchange, in a dye evaluation test, at 25° C. when 500 μg of said dye,about 500 μl of dichloromethane, 100 μl of pentamethyldisiloxane, and 10μl of a hydrosilation catalyst solution having between about 2 and 3weight percent platinum are mixed together.
 9. A curable compositionaccording to claim 8, wherein said compound having more than oneethylenically unsaturated group is aliphatic and comprises olefinic oracetylenic unsaturation.
 10. A curable composition according to claim 8,wherein said compound having more than one ethylenically unsaturatedgroup comprises a silicone backbone and at least two functional groupsselected from the group consisting of vinyl, allyl, butenyl, propenyl,isopropenyl, hexenyl, cyclohexenyl, cyclopentyl, cycloheptenyl andcyclooctenyl groups.
 11. A curable composition according to claim 8,wherein said compound having more than one ethylenically unsaturatedgroup has a weight average molecular weight between 4,000 and 150,000.12. A curable composition according to claim 8, wherein said crosslinkercompound comprises at least two SiH groups selected from the groupconsisting of organohydrosilanes, organohydrocyclopolysiloxanes,organohydropolysiloxanes, and branched organohydropolysiloxanes.
 13. Acurable composition according to claim 8, wherein said compositioncomprises a ratio of SiH groups to functional groups between 1:1 and10:1.
 14. A curable composition according to claim 8, wherein saidcatalyst is selected from the group consisting of: chloroplatinic acid;a complex of chloroplatinic acid and an alcohol; a complex of platinumand an olefin; a complex of platinum and a ketone; a complex of platinumand a vinylsiloxane; colloidal platinum, a complex of colloidal platinumand a vinylsiloxane; tetrakis (triphenylphosphine) palladium; a mixtureof palladium black and triphenylphosphine; rhodium or rhodium compoundcatalysts; radiation activated hydrosilation catalysts including (h⁴-cyclooctadiene)diarylplatinum complexes; (h⁵-cyclopentadienyl)trialkylplatinum complexes, and (h⁵-cyclopentadienyl)tri(s-aliphatic)-platinum complexes with a sensitizerthat is capable of absorbing visible light; and Platinum(II)b-diketonate complexes.
 15. A curable composition according to claim 8,wherein said catalyst comprises platinum and wherein said compositioncomprises a ratio of platinum to functional groups between 1:2 and1:1,000.
 16. A curable composition according to claim 8, wherein saidcatalyst is a Karsted catalyst, wherein said composition comprises aratio of platinum to functional groups between 1:2 and 1:1,000, andwherein said compound having more than one ethylenically unsaturatedgroup comprises a silicone backbone having two or more vinyl functionalgroups.
 17. A curable composition according to claim 8, wherein saidcure-indicating dye has a first color in the visible spectrum before thecure reaction is effected and is essentially colorless after the curereaction is effected.
 18. A curable composition according to claim 8,wherein said cure-indicating dye changes color to indicate the gel pointof said composition.
 19. A curable composition according to claim 10,wherein said cure-indicating dye changes color to indicate the set timeof said composition.
 20. A curable composition according to claim 8,wherein said cure-indicating dye changes color to indicate that thecomposition has finished evolving gas as a result of being cured.
 21. Acurable composition according to claim 8, wherein said compositionfurther comprises an additional cure-indicating dye that exhibits acolor change, in a dye evaluation test, at 25° C. when 500 μg of saiddye, about 500 μl of dichloromethane, 100 μl of pentamethyldisiloxane,and 10 μl of a hydrosilation catalyst solution having between about 2and 3 weight percent platinum are mixed together.
 22. A curablecomposition according to claim 8, wherein said cure-indicating dye ispresent in an amount at least 0.0001 weight percent.
 23. A curablecomposition according to claim 8, wherein said cure-indicating dye has amolar extinction coefficient of at least 10,000M⁻¹ cm⁻¹.
 24. A curablecomposition according to claim 10, wherein said cure-indicating dyeexhibits a loss of 90% in absorbance within about 10 minutes at 25° C.when 500 mg of said dye, about 500 ml of dichloromethane, 100 ml ofpentamethyldisiloxane and 10 ml of a hydrosilation catalyst solutionhaving between about 2 and 3 weight percent platinum are mixed togetheras compared to an identical solution that does not contain ahydrosilation catalyst.
 25. A curable composition according to claim 8,wherein said cure-indicating dye exhibits a loss of 99% in absorbancewithin about 10 minutes at 25° C. when 500 mg of said dye, about 500 mlof dichloromethane, 100 ml of pentamethyldisiloxane and 10 ml of ahydrosilation catalyst solution having between about 2 and 3 weightpercent platinum are mixed together as compared to an identical solutionthat does not contain a hydrosilation catalyst.
 26. A curablecomposition according to claim 16, wherein said cure-indicating dyeexhibits a transition time between the onset of color change and theeffective completion of the color change of less than three minutes at32° C.
 27. A curable composition according to claim 10, wherein saidcure-indicating dye is selected from the group consisting of indoanilinedyes, indophenol dyes, quinone monoimine dyes, quinone diimine dyes,cyanine dyes, merocyanine dyes, cyclohexadienone dyes,iminocyclohexadienone dyes, imidazolylidinecyclohexadienone dyes,dihydronaphthalenone dyes, iminodihydronaphthalenone dyes,imidazolylidinedihydronaphthalenone dyes, cyclohexadienimine dyes, arylsubstituted bis trifluoromethylsulfonylhexatrienyl dyes, arylsubstituted bis (trifluoromethylsulfonyl)butadienyl dyes, arylsubstituted bis (fluorosulfonyl)hexatrienyl dyes, aryl substituted bis(fluorosulfonyl)butadienyl dyes, oxazolone dyes, cationic dyes, anionicdyes and amphoteric dyes.
 28. A curable composition according to claim8, wherein said cure-indicating dye is selected from the groupconsisting of:4-[[4-(Dimethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;4-[[4-(Diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[4-(Dimethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[2-methyl-4-(diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;3-Methoxy-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Methyl-4-[[4-(4-morpholinyl)phenyl]-imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[4-(4-morpholinyl)-phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dimethyl-4-[[4-(4-morpholinyl)-phenyl]imino]-2,5-cyclohexadien-1-one;2,5-Dichloro-4-[[4-(diethylamino)-phenyl]imino]-2,5-cyclohexadien-1-one;3-Methoxy-4-[[3-methoxy-4-(diethyl-amino)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-[[4-(Diethylamino)-2-methylphenyl]imino]-6-oxo-N-phenyl-1,4-cyclohexadiene-1-carboxamide;5-[[4-(Diethylamino)-2-methylphenyl]imino]-8-(5H)-quinolinone;2,5-Dichloro-4-[[2-methyl-4-(diethylamino)-phenyl]imino]-2,5-cyclohexadiene-1-one;2,6-Dichloro-4-[[4-(acetamido)phenyl]imino]-2,5-cyclohexadiene-1-one;2,6-Dichloro-4-[4-ethoxy phenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(2-methyl-4-ethoxyphenyl)imino]-2,5-cyclohexadien-1-one; 2,6-Dimethyl-4-[4-hydroxyphenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(4-methoxy-1-naphthyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[4-(benzyloxy)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(2,4-dimethoxyphenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(4-methoxyphenyl)imino]-2,5-cyclohexadien-1-one;4-(phenylimino)-2,5-cyclohexadien-1-one;4-(1-naphthylimino)-2,5-cyclohexadien-1-one;4-(2-naphthylimino)-2,5-cyclohexadien-1-one;2,5-Bis(phenylamino)-4(phenylimino)-2,5-cyclohexadien-1-one;2,5-Dibromo-4-[(2,4-dibromophenyl)imino]-2,5-cyclohexadien-1-one;2,3,5-Trichloro-4-[(2,4,6-trichlorophenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4-[4-(dimethylamino)phenyl]-5-phenyl-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4,5-bis(4-hydroxyphenyl)-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Dimethoxy-4-[4,5-bis(2-furyl)-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Bis[1,1-(dimethyl)ethyl]-4-[4,5-bis(2-furyl)-(2H)-imidazol-2-ylidene]-2,5-cyclohexadien-1-one;4-(phenylimino)-2,5-cyclohexadien-1-imine;Mono[(3-methyl-2-(3H)-benzothiazolylidene)hydrazono]2,5-cyclohexadiene-1,4-dione;4-[(3-Chloro-4-oxo-2,5-cyclohexadien-1-ylidine)-amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-(3H)-pyrazol-3-one;4-[(3,5-Dichloro-4-oxo-2,5-cyclohexadiene-1-ylidine)amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-(3H)-pyrazol-3-one;3-[(3,5-Dichloro-4-oxo-2,5-cyclohexadien-1-ylidine)amino]-2,5-dihydro-4,5-dimethyl-1-phenylpyrrol-2-one;4-(Phenylsulfonyl)imino-1-[4-[(phenylsulfonyl)imino]-2,5-cyclohexadien-1-ylidenyl]-2,5-cyclohexadiene;4-[6,6-Bis[(trifluoromethyl)sulfonyl]-1,3,5-hexatrienyl]-N,N-dimethylbenzenamine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2-ethoxy-N,N-dimethylbenzenamine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,5-dimethoxy-N,N-dimethylbenzenamine;9-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,3,6,7-tetrahydro-(1H,5H)-benzo[ij]quinolizine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,6-N,N-tetramethyl-benzenamine;4-[5,5-Bis[(trifluoromethyl)sulfonyl]-2,4-pentadienylidene]-1,4-dihydro-1-methylquinoline;6,6-Bis[4-(dimethylamino)phenyl]1,3,5-hexatriene-1,1-bis(sulfonylfluoride);4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-N,N-dimethylbenzenamine;and4-[3-[4-(Dimethylamino)phenyl]-2-propenylidene]-2-phenyl-5(4H)-oxazolone;anionic dyes having the following anions:5-[5-(1,3-Diethylhexahydro-2,4,6-trioxo-5-pyrimidinyl)-2,4-pentadienylidene]-1,3-diethyl-2,4,6(1H,3H,5H)-pyrimidenetrione;and cationic dyes having the following cations or having the cations ofthe following cationic dyes: 3H-Indolium,3-[3-[4-(dimethylamino)phenyl]-2-propenylidene]-1-methyl-2-phenyl;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-[bis(2-chloroethyl)amino]phenyl]azo]-6-methoxy-;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-(diethylamino)phenyl]azo]-6-ethoxy-;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-(diethylamino)-2-methylphenyl]azo]-6-ethoxy-;C. I. Basic Blue 68; C. I. Basic Blue 76; C. I. Basic Blue 57; C. I.Basic Blue 60; Benzo[a]phenoxazin-7-ium, 9-(dimethylamino)-;2-[4,4,-bis[4-dimethylamino)phenyl]-1,3-butadienyl]-1-ethyl quinolinium;4-[4,4,-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]1-ethyl quinolinium;Naphtho[2,1-d]thiazolium,2-[4,4-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]-3-ethyl-;2-[2-[4-(dimethylamino)phenyl]ethenyl]-1-phenyl-3-methyl quinoxalinium;Quinolinium,2-[3-(5-chloro-1,3-dihydro-1,3,3-trimethyl-(2H)-indol-2-ylidene)-1-propenyl]-1-methyl-;Benzothiazolium, 2-[[4-(dimethylamino)phenyl]azo]-6-methoxy-3-methyl-;Benz[cd]indolium, 2-[4-(diethylamino)-2-ethoxyphenyl]-1-ethyl-;2-[p-(Dimethylamino)styryl]-1,3-dimethylquinoxalinium;2-[3-(5-chloro-1,3-dihydro-1,3,3-trimethyl-(2H)-indol-2-ylidene)-1-propenyl]-1-methylquinoxalinium;C. I. Basic Blue 40; Benzothiazolium,2-[[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-6-methoxy-3-methyl-;Benzothiazolium,2-[[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-6-methoxy-3-methyl-; C. I.Basic Blue 42; C. I. Basic Blue 53; 3H-Indolium,5-chloro-2-[5-(5-chloro-1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-1,3-pentadienyl]-1,3,3-trimethyl-;Basic Blue 142; Benz[cd]indolium,2-[2-(9-ethyl-(9H)-carbazol-3-yl)ethenyl]-1-methyl-; Benz[cd]indolium,2-[2-[4-(dimethylamino)phenyl]-2-phenylethenyl]-1-methyl-;Benz[cd]indolium, 2-[2,2-bis[4-(dimethylamino)phenyl]ethenyl]-1-methyl-;Benz[cd]indolium,2-[2-(2,3-dihydro-1-methyl-2-phenyl-1H-indol-3-yl)-2-(2-methylphenyl)ethenyl]-1-methyl-;Pyrimidinium, 4-[5-(2,3-dihydro-1,3-dimethyl-2-oxo-;4(1H)-pyrimidinylidene)-1,3-pentadienyl]-2,3-dihydro-1,3-dimethyl-2-oxo-;3H-Indolium,2-[[3-[(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)methyl]-5,5-dimethyl-2-cyclohexen-1-ylidene]methyl]-1,3,3-trimethyl-;Benz[cd]indolium,2-[2-[4-(diethylamino)-2-methylphenyl]ethenyl]-1-methyl-; 3H-Indolium,3-[3-[4-[(dimethylamino)phenyl]-2-propenylidene]-1-methyl-2-(4-methoxyphenyl)-;3H-Indolium,3-[(2,5-dimethyl-1-phenyl-(1H)-pyrrol-3-yl)methylene]-1,2-dimethyl-;3H-Indolium,3-[2,5-dimethyl-1-phenyl-(1H)-pyrrol-3-yl)methylene]-1-methyl-2-phenyl-;2-[2-[2-chloro-4-(dimethylamino)phenyl]ethenyl]-1-methylbenz[cd]indolium;C. I. Basic Violet 22; C. I. Basic Red 15; Benz[cd]indolium,2-[2-[4-(dimethylamino)phenyl]ethenyl]-1-methyl-;Benz[cd]indolium,2-[2-[4-(dimethylamino)-2-ethoxyphenyl]ethenyl]-1-methyl-;and 3H-Indolium,2-[1-cyano-4,4-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]-1,3,3-trimethyl-.29. A curable composition according to claim 8, wherein saidcure-indicating dye is selected from the group consisting of: neutraldyes represented by the following general formula: ##STR41## wherein:each R¹, R², R³, and R⁴ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group, and wherein R¹and R² or R³ and R⁴ may be connected to form a saturated or unsaturatedring;A is O, S, or NR²², wherein R²² is hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group; and B is anygroup capable of providing extended conjugation thereby rendering thedye capable of absorbing visible, near-UV, or near-infrared radiationincluding groups of formula D, E, F, H, or J, wherein D is representedby formula: ##STR42## wherein: each R⁵, R⁶, R⁷, R⁸, and R⁹ group isindependently hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group and wherein any two adjacent R⁵, R⁶, R⁷, R⁸, and R⁹groups may be connected to form a ring; E is represented by formula:##STR43## wherein: X¹ is C(R¹²)₂, S, NR¹², or O; X² is C(R¹²)₂, S, NR¹²,or O; and each R¹⁰, R¹¹ and R¹² group is independently hydrogen, ahydrocarbyl-containing group, or a heterocyclic group and wherein R¹⁰and R¹¹ may be connected to form a ring; F is represented by formula:##STR44## wherein: X³ is N or CR¹⁶ ; and each R¹³, R¹⁴, R¹⁵, and R¹⁶group is independently hydrogen, halogen, a hydrocarbyl-containinggroup, or a heterocyclic group and wherein any two adjacent R¹³, R¹⁴,R¹⁵, and R¹⁶ groups may be connected to form a ring; H is represented byformula: ##STR45## wherein: each R²⁰ and R²¹ group is independentlyhydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclicgroup and wherein R²⁰ and R²¹ may be connected to form a ring; and J isrepresented by formula: ##STR46## wherein: each R⁵, R⁶, R⁷ and R⁸ groupis independently hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group and wherein any two R⁵, R⁶, R⁷ and R⁸ groups may beconnected to form a ring; and R²³ is hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group;sulfonyl dyesrepresented by the following general formula: ##STR47## wherein: eachR²⁴ and R²⁵ group is independently hydrogen, a hydrocarbyl-containinggroup, or a heterocyclic group with the proviso that at least one of R²⁴and R²⁵ is or contains a substituted aryl, aminoaryl or heterocyclicgroup; each R²⁶ and R²⁷ group is independently a --(CF₂)_(m) F groupwherein m is a number between 0 and 20; and n is an integer less than5;neutral dyes represented by the following general formula: ##STR48##wherein: each R¹, R², R³, R⁴, and R²⁹ group is independently hydrogen,halogen, a hydrocarbyl-containing group, or a heterocyclic group, andwherein any two adjacent R¹, R², R³, R⁴, or R²⁹ groups may be connectedto form a ring; and R³⁰ is hydrogen, halogen, a hydrocarbyl-containinggroup, or a heterocyclic group and n is an integer less than 5;anionicdyes having the following general formula: ##STR49## wherein: Zrepresents the non-metallic atoms necessary to complete a substituted orunsubstituted nitrogen-containing heterocyclic ring; each R²⁸ isindependently hydrogen, a hydrocarbyl-containing group, or aheterocyclic group; n is an integer less than 5; and wherein M+ isselected from any suitable cation;cationic dyes having the followinggeneral formula: ##STR50## wherein: each R³¹, R³², R³³, and R³⁴ group isindependently hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group, and wherein any two adjacent R³¹, R³², R³³, or R³⁴groups may be connected to form a ring; R³⁵ and R³⁶ are as defined abovefor R³³ and R³⁴ ; X is O, S, or NR³⁷ ; Y is N or CR³⁸ ; R³⁷ and R³⁸ areas defined above for R³³ ; and wherein M- is any suitable anion;cationicdyes having the following general formula: ##STR51## wherein: each R³¹,R³², R³³, R³⁴ and R⁴⁰ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group, and wherein anytwo adjacent R³¹, R³², R³³, or R³⁴ groups may be connected to form aring; R³⁹ is independently hydrogen, a hydrocarbyl-containing group, ora heterocyclic group; X is C═R⁴⁸, C(R³⁸)₂, O, S, or NR³⁷, wherein R³⁷ isas defined above for R³⁹, R³⁸ is as defined above for R⁴⁰, R⁴⁸ is an oxogroup, a divalent hydrocarbyl-containing group or a divalentheterocyclic group, and wherein R⁴⁸ and R³⁴ may be connected to form anunsaturated ring, and R³⁷ and R³⁴ may be connected to form a ring; andwherein M- is any suitable anion; andcationic dyes having the followinggeneral formula: ##STR52## wherein: each R⁴² to R⁴⁷ group isindependently hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group; each R⁴⁰, R⁴¹, R⁴⁶, and R⁴⁷ group is independentlyhydrogen, a hydrocarbyl-containing group, or a heterocyclic group andwherein any two adjacent R⁴¹ to R⁴³ and R⁴⁴ to R⁴⁶ groups may form aring; n is an integer less than 5; and wherein M- is any suitable anion.30. A curable composition according to claim 8, wherein saidcure-indicating dye is selected from the group consisting of4-[[4-(Dimethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;4-[[4-(Diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[4-(Dimethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[2-methyl-4-(diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;3-Methoxy-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Methyl-4-[[4-(4-morpholinyl)phenyl]imino]-2,5-cyclohexadien-1-one;2,5-Dichloro-4-[[4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-[[4-(Diethylamino)-2-methylphenyl]imino]-6-oxo-N-phenyl-1,4-cyclohexadiene-1-carboxamide;5-[[4-(Diethylamino)-2-methylphenyl]imino]-8-(5H)-quinolinone;2,6-Dichloro-4-[[4-(acetamido)phenyl]imino]-2,5-cyclohexadien-1-one;4-(1-naphthylimino)-2,5-cyclohexadien-1-one;4-(2-naphthylimino)-2,5-cyclohexadien-1-one;2,5-Bis(phenylamino)-4(phenylimino)-2,5-cyclohexadien-1-one;4-[5,5-Bis[(trifluoromethyl)sulfonyl]-2,4-pentadienylidene]-1,4-dihydro-1-methylquinoline;6,6-Bis[4-(dimethylamino)phenyl]1,3,5-hexatriene-1,1-bis(sulfonylfluoride);4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-N,N-dimethylbenzenamine;and4-[3-[4-(Dimethylamino)phenyl]-2-propenylidene]-2-phenyl-5(4H)-oxazolone.31. A curable composition according to claim 8, wherein said compositionis in the form of a coating on a substrate.
 32. A curable compositionaccording to claim 8, wherein said composition exhibits a color changeupon curing of at least 10 ΔE* units.
 33. A curable composition,comprising:an ethylenic compound comprising a silicone backbone havingtwo or more vinyl functional groups; a crosslinker compound comprisingat least two SiH groups and being selected from the group consisting oforganohydrosilanes, organohydrocyclopolysiloxanes,organohydropolysiloxanes, and branched organohydropolysiloxanes; acatalyst capable of catalyzing a hydrosilation reaction, wherein saidcatalyst comprises a complex of platinum and a vinylsiloxane and whereinsaid composition comprises a molar ratio of platinum to vinyl functionalgroups between 1:2 and 1:1,000; and a cure-indicating dye that exhibitsa color change within about 10 minutes at 25° C. when 500 mg of saiddye, about 500 ml of dichloromethane, 100 ml of pentamethyldisiloxane,and 10 ml of a hydrosilation catalyst solution having between about 2and 3 weight percent platinum are mixed together, wherein saidcure-indicating dye is selected from the group consisting of indoanilinedyes, indophenol dyes, quinone monoimine dyes, quinone diimine dyes,cyanine dyes, merocyanine dyes, cyclohexadieneone dyes,iminocyclohexadieneone dyes, imidazolylidinecyclohexadienone dyes,dihydronaphthalenone dyes, iminodihydronaphthalenone dyes,imidazolylidinedihydronaphthalenone dyes, cyclohexadienimine dyes, arylsubstituted bis (trifluoromethylsulf-onyl)hexatrienyl dyes, arylsubstituted bis (trifluoromethylsulfonyl)butadienyl dyes, arylsubstituted bis (fluorosulfonyl)hexatrienyl dyes, aryl substituted bis(fluorosulfonyl)butadienyl dyes, oxazolone dyes, cationic dyes, anionicoxonol dyes and betaine dyes.
 34. A curable composition, comprising:anethylenic compound comprising a silicone backbone having two or morevinyl functional groups; a crosslinker compound comprising at least twoSiH groups and being selected from the group consisting oforganohydrosilanes, organohydrocyclopolysiloxanes,organohydropolysiloxanes, and branched organohydropolysiloxanes; acatalyst capable of catalyzing a hydrosilation reaction, wherein saidcatalyst comprises platinum and wherein said composition comprises amolar ratio of platinum to functional groups between 1:2 and 1:1,000;and a cure-indicating dye that exhibits a color change within about 10minutes at 25° C. when 500 mg of said dye, about 500 ml ofdichloromethane, 100 ml of pentamethyldisiloxane, and 10 ml of ahydrosilation catalyst solution having between about 2 and 3 weightpercent platinum are mixed together, wherein said cure-indicating dye isselected from the group consisting of: neutral dyes represented by thefollowing general formula: ##STR53## wherein: each R¹, R², R³, and R⁴group is independently selected from the group consisting of: hydrogen,halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆-C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²), and wherein R¹ and R²or R³ and R⁴ may be connected to form a ring; A is O or NR²², whereinR²² is a group selected from the group consisting of: hydrogen, a C₁-C₂₀ alkyl, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₂ -C₁₈ alkenyl, aC₆ -C₁₈ arylamino, and substituted sulfonyl; and B is any group capableof providing extended conjugation thereby rendering the dye capable ofabsorbing visible, near-UV, or near-infrared radiation including groupsof formula D, E, F, H, or J, wherein D is represented by formula:##STR54## wherein: each R⁵, R⁶, R⁷, R⁸, and R⁹ group is independentlyselected from the group consisting of: hydrogen, halogen, a C₁ -C₂₀alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino,morpholino, and alkylamido and wherein any two adjacent R⁵, R⁶, R⁷, R⁸,and R⁹ groups may be connected to form a ring; E is represented byformula: ##STR55## wherein: X¹ is S or O; X² is C(R¹²)₂ or NR¹² ; andeach R¹⁰, R¹¹ and R¹² group is independently selected from the groupconsisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, aC₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, and wherein R¹⁰ and R¹¹ may be connected to form aring; F is represented by formula: ##STR56## wherein: X³ is N or CR¹⁶ ;and each R¹³, R¹⁴, R¹⁵, and R¹⁶ group is independently selected from thegroup consisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆-C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂-C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino and wherein any two adjacentR¹³, R¹⁴, R¹⁵, and R¹⁶ groups may be connected to form a ring; H isrepresented by formula: ##STR57## wherein: each R²⁰ and R²¹ group isindependently selected from the group consisting of: hydrogen, halogen,a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl,a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆-C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino,morpholino, and furyl and wherein R²⁰ and R²¹ may be connected to form aring; and J is represented by formula: ##STR58## wherein: each R⁵, R⁶,R⁷ and R⁸ group is independently selected from the group consisting of:hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, aC₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, morpholino, alkylamido and wherein R⁵ and R⁶ or R⁷and R⁸ may be connected to form a ring; and R²³ is a group selected fromthe group consisting of: hydrogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, aC₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈hydroxyaryl, a C₆ -C₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl,a C₂ -C₂₀ di(hydrocarbyl)amino, and substituted sulfonyl;sulfonyl dyesrepresented by the following general formula: ##STR59## wherein: eachR²⁴ and R²⁵ group is independently selected from the group consistingof: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, aC₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino with the proviso that at least one of R²⁴ and R²⁵is or contains a substituted aryl, aminoaryl or heterocyclic group; eachR²⁶ and R²⁷ group is independently selected from the group consistingof: F and CF₃ ; and n is 0 to 3;neutral dyes represented by thefollowing general formula: ##STR60## wherein: each R¹, R², R³, R⁴, andR²⁹ group is independently selected from the group consisting of:hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, aC₆ -C₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²), and wherein any twoadjacent R¹, R², R³, R⁴, or R²⁹ groups may be connected to form a ring;R³⁰ is a group selected from the group consisting of: hydrogen, halogen,a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl,a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆-C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino; and n is1 or 2;anionic oxonol dyes having the following general formula:##STR61## wherein: Z represents the non-metallic atoms necessary tocomplete a substituted or unsubstituted nitrogen-containing heterocyclicring, each R²⁸ is independently selected from the group consisting of:hydrogen, a C₁ -C₂₀ alkyl, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆-C₁₈ hydroxyaryl, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₆ -C₁₈aminoaryl; n is 1 or 2; and wherein M+ is selected from any suitablecation;cationic dyes having the following general formula: ##STR62##wherein: each R³¹, R³², R³³, and R³⁴ group is independently selectedfrom the group consisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁-C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, aC₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂-C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²),and wherein any two adjacent R³¹, R³², R³³, or R³⁴ groups may beconnected to form a ring; R³⁵ and R³⁶ are as defined above for R³³ andR³⁴ ; X is O or NR³⁷ ; Y is N or CR³⁸ ; R³⁷ and R³⁸ are as defined abovefor R³³ ; and wherein M- is any suitable anion;cationic dyes having thefollowing general formula: ##STR63## wherein: each R³¹, R³², R³³, andR³⁴ group is independently selected from the group consisting of:hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, aC₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀di(hydrocarbyl)amino, carboxamide (--C(O)NR¹ R²), and wherein any twoadjacent R³¹, R³², R³³, or R³⁴ groups may be connected to form a ring;each R³⁹ is independently selected from the group consisting of:hydrogen, a C₁ -C₂₀ alkyl, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆-C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, a C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino; R⁴⁰ isindependently selected from the group consisting of: hydrogen, halogen,a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl,a C₆ -C₁₈ aryloxy, a C₆ -C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆-C₁₈ carboxyaryl, a C₂ -C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈arylamino, C₆ -C₁₈ aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino, andcarboxamide; X is C═R⁴⁸, C(R³⁸)₂ or S, wherein R³⁸ is as defined abovefor R⁴⁰ ; R⁴⁸ is an oxo group, a divalent hydrocarbyl-containing group,or a divalent heterocyclic group; and wherein R⁴⁸ and R³⁴ may beconnected to form an unsaturated ring; and wherein M- is any suitableanion;cationic dyes having the following general formula: ##STR64##wherein: each R⁴² to R⁴⁵ group is independently selected from the groupconsisting of: hydrogen, halogen, a C₁ -C₂₀ alkyl, a C₁ -C₂₀ alkoxy, aC₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆ -C₁₈hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂ -C₁₈alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈ aminoaryl,a C₂ -C₂₀ di(hydrocarbyl)amino; each R⁴⁰, R⁴¹, R⁴⁶ and R⁴⁷ group isindependently selected from the group consisting of: hydrogen, a C₁ -C₂₀alkyl, a C₃ -C₁₈ cycloalkyl, a C₆ -C₁₈ aryl, a C₆ -C₁₈ aryloxy, a C₆-C₁₈ hydroxyaryl, a C₆ -C₁₈ arylcarboxy, a C₆ -C₁₈ carboxyaryl, a C₂-C₁₈ alkenyl, a C₁ -C₂₀ alkylamino, a C₆ -C₁₈ arylamino, a C₆ -C₁₈aminoaryl, a C₂ -C₂₀ di(hydrocarbyl)amino and wherein any two adjacentR⁴¹ to R⁴³ and R⁴⁴ to R⁴⁶ groups may be connected to form a ring; n is 1or 2; and wherein M- is any suitable anion.
 35. A curable composition,comprising:an ethylenic compound comprising a silicone backbone havingtwo or more vinyl functional groups; a crosslinker compound comprisingat least two SiH groups and being selected from the group consisting oforganohydrosilanes, organohydrocyclopolysiloxanes,organohydropolysiloxanes, and branched organohydropolysiloxanes, whereinsaid composition comprises a ratio of SiH groups to functional groupsbetween 1:1 and 10:1; a catalyst capable of catalyzing a hydrosilationreaction, wherein said catalyst comprises platinum and wherein saidcomposition comprises a ratio of platinum to functional groups between1:2 and 1:1,000; and a cure-indicating dye selected from the groupconsisting of4-[[4-(Dimethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;4-[[4-(Diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[4-(Dimethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[2-methyl-4-(diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;3-Methoxy-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Methyl-4-[[4-(4-morpholinyl)phenyl]imino]-2,5-cyclohexadien-1-one;2,5-Dichloro-4-[[4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-[[4-(Diethylamino)-2-methylphenyl]imino]-6-oxo-N-phenyl-1,4-cyclohexadiene-1-carboxamide;5-[[4-(Diethylamino)-2-methylphenyl]imino]-8-(5H)-quinolinone;2,6-Dichloro-4-[[4-(acetamido)phenyl]imino]-2,5-cyclohexadien-1-one;4-(1-naphthylimino)-2,5-cyclohexadien-1-one;4-(2-naphthylimino)-2,5-cyclohexadien-1-one;2,5-Bis(phenylamino)-4(phenylimino)-2,5-cyclohexadien-1-one;4-[5,5-Bis[(trifluoromethyl)sulfonyl]-2,4-pentadienylidene]-1,4-dihydro-1-methylquinoline;6,6-Bis[4-(dimethylamino)phenyl]1,3,5-hexatriene-1,1-bis(sulfonylfluoride);4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-N,N-dimethylbenzenamine;and4-[3-[4-(Dimethylamino)phenyl]-2-propenylidene]-2-phenyl-5(4H)-oxazolone.36. A silicone composition comprising:a curable silicone polymercontaining at least two functional groups capable of reacting with a SiHgroup in the presence of a catalyst; a crosslinker compound containingat least two SiH groups; a hydrosilation catalyst; and one or morecure-indicating dyes that exhibit a color change within about 10 minutesat 25° C. when 500 mg of said dye, about 500 ml of dichloromethane, 100ml of pentamethyldisiloxane, and 10 ml of a hydrosilation catalystsolution having between about 2 and 3 weight percent platinum are mixedtogether.
 37. A silicone composition according to claim 36, wherein saidcurable silicone polymer comprises vinyl functional groups.
 38. Asilicone composition according to claim 37, wherein said curablesilicone polymer has a weight average molecular weight between 1,000 and450,000.
 39. A silicone composition according to claim 36, wherein saidcurable silicone polymer has a weight average molecular weight between4,000 and 150,000.
 40. A silicone composition according to claim 37,wherein said curable silicone polymer has the formula: ##STR65## whereinR¹ and R² are vinyl and n has a value between about 50 and 2,000.
 41. Asilicone composition according to claim 36, wherein said curablesilicone polymer has the formula: ##STR66## wherein at least two but notmore than one-half of all the R¹ groups in said polymer comprise afunctional group selected from the group consisting of vinyl, allyl,butenyl, propenyl, isopropenyl, hexenyl, cyclohexenyl, cyclopentyl,cycloheptenyl and cyclooctenyl groups, and the remainder of said R¹groups comprise a group that will not react with SiH compounds in thepresence of a catalyst; and wherein m represents 0, 1, 2, or 3, and nrepresents a number having an average value from 1 to about 10,000. 42.A silicone composition according to claim 39, wherein said crosslinkercompound is selected from the group consisting of organohydrosilanes,organohydrocyclopolysiloxanes, organohydropolysiloxanes, and branchedpolyorganohydropolysiloxanes.
 43. A silicone composition according toclaim 37, wherein said composition comprises a ratio of SiH groups tofunctional groups between 1.3:1 and 4:1.
 44. A silicone compositionaccording to claim 37, wherein said hydrosilation catalyst is selectedfrom the group consisting of: chloroplatinic acid, a complex ofchloroplatinic acid and an alcohol, a complex of platinum and an olefin,a complex of platinum and a ketone, a complex of platinum and avinylsiloxane, colloidal platinum, a complex of colloidal platinum and avinylsiloxane; tetrakis (triphenylphosphine) palladium, a mixture ofpalladium black and triphenylphosphine; rhodium or rhodium compoundcatalysts; radiation activated hydrosilation catalysts including (h⁴-cyclooctadiene)diarylplatinum complexes, (h⁵-cyclopentadienyl)trialkylplatinum complexes, and (h⁵-cyclopentadienyl)tri(s-aliphatic)-platinum complexes with a sensitizerthat is capable of absorbing visible light; and Pt(II) B-diketonatecomplexes.
 45. A silicone composition according to claim 44, whereinsaid hydrosilation catalyst comprises platinum and wherein saidcomposition comprises a ratio of platinum to functional groups between1:2 and 1:1,000.
 46. A silicone composition according to claim 43,wherein said hydrosilation catalyst comprises a Karstedt catalyst.
 47. Asilicone composition according to claim 36, wherein said composition hasa first color in the visible spectrum before the cure reaction iseffected and a second different color after the cure reaction iseffected.
 48. A silicone composition according to claim 47, wherein thedifference between said first color and said second color is visible tothe naked eye.
 49. A silicone composition according to claim 47, whereinthe difference between said first color and said second color isdetectable by the human eye when referenced to an external colorstandard which matches either said first or said second color.
 50. Asilicone composition according to claim 46, wherein said cure-indicatingdye changes color to indicate the gel point of said composition.
 51. Asilicone composition according to claim 46, wherein said cure-indicatingdye changes color to indicate the set time of said composition.
 52. Asilicone composition according to claim 36, wherein said compositionfurther comprises an additional cure-indicating dye.
 53. A siliconecomposition according to claim 43, wherein said cure-indicating dye ispresent in an amount at least 0.0001 weight percent.
 54. A siliconecomposition according to claim 36, wherein said cure-indicating dye hasa molar extinction coefficient of at least 10,000 M⁻¹ cm⁻¹.
 55. Asilicone composition according to claim 36, wherein said cure-indicatingdye is selected from the group consisting of indoaniline dyes,indophenol dyes, quinone monoimine dyes, quinone diimine dyes, cyaninedyes, merocyanine dyes, cyclohexadienone dyes, iminocyclohexadienonedyes, imidazolylidinecyclohexadienone dyes, dihydronaphthalenone dyes,iminodihydronaphthalenone dyes, imidazolylidinedihydronaphthalenonedyes, cyclohexadienimine dyes, aryl substituted bistrifluoromethylsulfonylhexatrienyl dyes, aryl substituted bis(trifluoromethylsulfonyl)butadienyl dyes, aryl substituted bis(fluorosulfonyl)hexatrienyl dyes, aryl substituted bis(fluorosulfonyl)butadienyl dyes, oxazolone dyes, cationic dyes, anionicdyes and amphoteric dyes.
 56. A silicone composition according to claim36, wherein said cure-indicating dye is selected from the groupconsisting of: neutral dyes represented by the following generalformula: ##STR67## wherein: each R¹, R², R³, and R⁴ group isindependently hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group, and wherein R¹ and R² or R³ and R⁴ may be connectedto form a saturated or unsaturated ring;A is O, S, or NR²², wherein R²²is hydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclicgroup; and B is any group capable of providing extended conjugationthereby rendering the dye capable of absorbing visible, near-UV, ornear-infrared radiation including groups of formula D, E, F, H, or J,wherein D is represented by formula: ##STR68## wherein: each R⁵, R⁶, R⁷,R⁸, and R⁹ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group and wherein anytwo adjacent R⁵, R⁶, R⁷, R⁸, and R⁹ groups may be connected to form aring; E is represented by formula: ##STR69## wherein: X¹ is C(R¹²)₂, S,NR¹², or O; X² is C(R¹²)₂, S, NR¹², or O; and each R¹⁰, R¹¹ and R¹²group is independently hydrogen, a hydrocarbyl-containing group, or aheterocyclic group and wherein R¹⁰ and R¹¹ may be connected to form aring; F is represented by formula: ##STR70## wherein: X³ is N or CR¹⁶ ;and each R¹³, R¹⁴, R¹⁵, and R¹⁶ group is independently hydrogen halogen,a hydrocarbyl-containing group, or a heterocyclic group and wherein anytwo adjacent R¹³, R¹⁴, R¹⁵, and R¹⁶ groups may be connected to form aring; H is represented by formula: ##STR71## wherein: each R²⁰ and R²¹group is independently hydrogen, halogen, a hydrocarbyl-containinggroup, or a heterocyclic group and wherein R²⁰ and R²¹ may be connectedto form a ring; and J is represented by formula: ##STR72## wherein: eachR⁵, R⁶, R⁷ and R⁸ group is independently hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group and wherein anytwo R⁵, R⁶, R⁷ and R⁸ groups may be connected to form a ring; and R²³ ishydrogen, halogen, a hydrocarbyl-containing group, or a heterocyclicgroup;sulfonyl dyes represented by the following general formula:##STR73## wherein: each R²⁴ and R²⁵ group is independently hydrogen, ahydrocarbyl-containing group, or a heterocyclic group with the provisothat at least one of R²⁴ and R²⁵ is or contains a substituted aryl,aminoaryl or heterocyclic group; each R²⁶ and R²⁷ group is independentlya --(CF₂)_(m) F group wherein m is a number between 0 and 20; and n isan integer less than 5;neutral dyes represented by the following generalformula: ##STR74## wherein: each R¹, R², R³, R⁴, and R²⁹ group isindependently hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group, and wherein any two adjacent R¹, R², R³, R⁴, or R²⁹groups may be connected to form a ring; and R³⁰ is hydrogen, halogen, ahydrocarbyl-containing group, or a heterocyclic group and n is aninteger less than 5;anionic dyes having the following general formula:##STR75## wherein: Z represents the non-metallic atoms necessary tocomplete a substituted or unsubstituted nitrogen-containing heterocyclicring; each R²⁸ is independently hydrogen, a hydrocarbyl-containinggroup, or a heterocyclic group; n is an integer less than 5; and whereinM+ is selected from any suitable cation;cationic dyes having thefollowing general formula: ##STR76## wherein: each R³¹, R³², R³³, andR³⁴ group is independently hydrogen, halogen, a hydrocarbyl-containinggroup, or a heterocyclic group, and wherein any two adjacent R³¹, R³²,R³³, or R³⁴ groups may be connected to form a ring; R³⁵ and R³⁶ are asdefined above for R³³ and R³⁴ ; X is O, S, or NR³⁷ ; Y is N or CR³⁸ ;R³⁷ and R³⁸ are as defined above for R³³ ; and wherein M- is anysuitable anion;cationic dyes having the following general formula:##STR77## wherein: each R³¹, R³², R³³, R³⁴ and R⁴⁰ group isindependently hydrogen, halogen, a hydrocarbyl-containing group, or aheterocyclic group, and wherein any two adjacent R³¹, R³², R³³, or R³⁴groups may be connected to form a ring; R³⁹ is independently hydrogen, ahydrocarbyl-containing group, or a heterocyclic group; X is C═R⁴⁸,C(R³⁸)₂, O, S, or NR³⁷, wherein R³⁷ is as defined above for R³⁹, R³⁸ isas defined above for R⁴⁰ ; R⁴⁸ is an oxo group, a divalenthydrocarbyl-containing group or a divalent heterocyclic group, andwherein R⁴⁸ and R³⁴ may be connected to form an unsaturated ring, andR³⁷ and R³⁴ may be connected to form a ring; and wherein M- is anysuitable anion; andcationic dyes having the following general formula:##STR78## wherein: each R⁴² to R⁴⁷ group is independently hydrogen,halogen, a hydrocarbyl-containing group, or a heterocyclic group; eachR⁴⁰, R⁴¹, R⁴⁶, and R⁴⁷ group is independently hydrogen, ahydrocarbyl-containing group, or a heterocyclic group and wherein anytwo adjacent R⁴¹ to R⁴³ and R⁴⁴ to R⁴⁶ groups may be connected to form aring; n is an integer less than 5; and wherein M- is any suitable anion,and wherein said dental impression material exhibits a color change uponcuring of at least 10 ΔE* units.
 57. A silicone composition according toclaim 36, wherein said cure-indicating dye is selected from the groupconsisting of4-[[4-(Dimethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;4-[[4-(Diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[4-(Dimethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;4-[[2-methyl-4-(diethylamino)phenyl]imino]-1,4-dihydronaphthalen-1-one;3-Methoxy-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Methyl-4-[[4-(4-morpholinyl)phenyl]-imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[4-(4-morpholinyl)-phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dimethyl-4-[[4-(4-morpholinyl)-phenyl]imino]-2,5-cyclohexadien-1-one;2,5-Dichloro-4-[[4-(diethylamino)-phenyl]imino]-2,5-cyclohexadien-1-one;3-Methoxy-4-[[3-methoxy-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-[[4-(Diethylamino)-2-methylphenyl]imino]-6-oxo-N-phenyl-1,4-cyclohexadiene-1-carboxamide;5-[[4-(Diethylamino)-2-methylphenyl]imino]-8-(5H)-quinolinone;2,5-Dichloro-4-[[2-methyl-4-(diethylamino)-phenyl]imino]-2,5-cyclohexadiene-1-one;2,6-Dichloro-4-[[4-(acetamido)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4-ethoxy phenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(2-methyl-4-ethoxyphenyl)imino]-2,5-cyclohexadien-1-one; 2,6-Dimethyl-4-[4-hydroxyphenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(4-methoxy-1-naphthyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[[4-(benzyloxy)phenyl]imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(2,4-dimethoxyphenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[(4-methoxyphenyl)imino]-2,5-cyclohexadien-1-one;4-(phenylimino)-2,5-cyclohexadien-1-one;4-(1-naphthylimino)-2,5-cyclohexadien-1-one;4-(2-naphthylimino)-2,5-cyclohexadien-1-one;2,5-Bis(phenylamino)-4(phenylimino)-2,5-cyclohexadien-1-one;2,5-Dibromo-4-[(2,4-dibromophenyl)imino]-2,5-cyclohexadien-1-one;2,3,5-Trichloro-4-[(2,4,6-trichlorophenyl)imino]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4-[4-(dimethylamino)phenyl]-5-phenyl-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Dichloro-4-[4,5-bis(4-hydroxyphenyl)-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Dimethoxy-4-[4,5-bis(2-furyl)-(2H)-imidazol-2-ylidine]-2,5-cyclohexadien-1-one;2,6-Bis[1,1-(dimethyl)ethyl]-4-[4,5-bis(2-furyl)-(2H)-imidazol-2-ylidene]-2,5-cyclohexadien-1-one;4-(phenylimino)-2,5-cyclohexadien-1-imine;Mono[(3-methyl-2-(3H)-benzothiazolylidene)hydrazono]2,5-cyclohexadiene-1,4-dione;4-[(3-Chloro-4-oxo-2,5-cyclohexadien-1-ylidine)amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-(3H)-pyrazol-3-one;4-[(3,5-Dichloro-4-oxo-2,5-cyclohexadien-1-ylidine)amino]-1,2-dihydro-1,5-dimethyl-2-phenyl-(3H)-pyrazol-3-one;3-[(3,5-Dichloro-4-oxo-2,5-cyclohexadien-1-ylidine)amino]-2,5-dihydro-4,5-dimethyl-1-phenylpyrrol-2one;4-(Phenylsulfonyl)imino-1-[4-[(phenylsulfonyl)imino]-2,5-cyclohexadien-1-ylidenyl]-2,5-cyclohexadiene;4-[6,6-Bis[(trifluoromethyl)sulfonyl]-1,3,5-hexatrienyl]-N,N-dimethylbenzenamine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2-ethoxy-N,N-dimethylbenzenamine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,5-dimethoxy-N,N-dimethylbenzenamine;9-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,3,6,7-tetrahydro-(1H,5H)-benzo[ij]quinolizine;4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-2,6-N,N-tetramethyl-benzenamine;4-[5,5-Bis[(trifluoromethyl)sulfonyl]-2,4-pentadienylidene]-1,4-dihydro-1-methylquinoline;6,6-Bis[4-(dimethylamino)phenyl]1,3,5-hexatriene-1,1-bis(sulfonylfluoride);4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-N,N-dimethylbenzenamine;and4-[3-[4-(Dimethylamino)phenyl]-2-propenylidene]-2-phenyl-5(4H)-oxazolone;anionic dyes having the following anions:5-[5-(1,3-Diethylhexahydro-2,4,6-trioxo-5-pyrimidinyl)-2,4-pentadienylidene]-1,3-diethyl-2,4,6(1H,3H,5H)-pyrimidenetrione;and cationic dyes having the following cations or having the cations ofthe following cationic dyes: 3H-Indolium,3-[3-[4-(dimethylamino)phenyl]-2-propenylidene]-1-methyl-2-phenyl;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-[bis(2-chloroethyl)amino]phenyl]azo]-6-methoxy-;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-(diethylamino)phenyl]azo]-6-ethoxy-;Benzothiazolium,3-(3-amino-3-oxopropyl)-2-[[4-(diethylamino)-2-methylphenyl]azo]-6-ethoxy-;C.I. Basic Blue 68; C.I. Basic Blue 76; C.I. Basic Blue 57; C.I. BasicBlue 60; Benzo[a]phenoxazin-7-ium, 9-(dimethylamino)-;2-[4,4,-bis[4-dimethylamino)phenyl]-1,3-butadienyl]-1-ethyl quinolinium;4-[4,4,-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]1-ethyl quinolinium;Naphtho[2,1-d]thiazolium,2-[4,4-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]-3-ethyl-;2-[2-[4-(dimethylamino)phenyl]ethenyl]-1-phenyl-3-methyl quinoxalinium;Quinolinium,2-[3-(5-chloro-1,3-dihydro-1,3,3-trimethyl-(2H)-indol-2-ylidene)-1-propenyl]-1-methyl-;Benzothiazolium, 2-[[4-(dimethylamino)phenyl]azo]-6-methoxy-3-methyl-;Benz[cd]indolium, 2-[4-(diethylamino)-2-ethoxyphenyl]-1-ethyl-;2-[p-(Dimethylamino)styryl]-1,3-dimethylquinoxalinium;2-[3-(5-chloro-1,3-dihydro-1,3,3-trimethyl-(2H)-indol-2-ylidene)-1-propenyl]-1-methylquinoxalinium;C.I. Basic Blue 40; Benzothiazolium,2-[[4-[ethyl(2-hydroxyethyl)amino]phenyl]azol-6-methoxy-3-methyl-;Benzothiazolium,2-[[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-6-methoxy-3-methyl-; C. I.Basic Blue 42; C. I. Basic Blue 53; 3H-Indolium,5-chloro-2-[5-(5-chloro-1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-1,3-pentadienyl]-1,3,3-trimethyl-;Basic Blue 142; Benz[cd]indolium,2-[2-(9-ethyl-(9H)-carbazol-3-yl)ethenyl]-1-methyl-; Benz[cd]indolium,2-[2-[4-(dimethylamino)phenyl]-2-phenylethenyl]-1-methyl-;Benz[cd]indolium, 2-[2,2-bis[4-(dimethylamino)phenyl]ethenyl]-1-methyl-;Benz[cd]indolium,2-[2-(2,3-dihydro-1-methyl-2-phenyl-1H-indol-3-yl)-2-(2-methylphenyl)ethenyl]-1-methyl-;Pyrimidinium, 4-[5-(2,3-dihydro-1,3-dimethyl-2-oxo-;4(1H)-pyrimidinylidene)-1,3-pentadienyl]-2,3-dihydro-1,3-dimethyl-2-oxo-;3H-Indolium,2-[[3-[(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)methyl]-5,5-dimethyl-2-cyclohexen-1-ylidene]methyl]-1,3,3-trimethyl-;Benz[cd]indolium,2-[2-[4-(diethylamino)-2-methylphenyl]ethenyl]-1-methyl-; 3H-Indolium,3-[3-[4-[(dimethylamino)phenyl]-2-propenylidene]-1-methyl-2-(4-methoxyphenyl)-;3H-Indolium,3-[(2,5-dimethyl-1-phenyl-(1H)-pyrrol-3-yl)methylene]-1,2-dimethyl-;3H-Indolium,3-[2,5-dimethyl-1-phenyl-(1H)-pyrrol-3-yl)methylene]-1-methyl-2-phenyl-;2-[2-[2-chloro-4-dimethylamino)phenyl]ethenyl]-1-methylbenz[cd]indolium;C. I. Basic Violet 22; C. I. Basic Red 15; Benz[cd]indolium,2-[2-[4-(dimethylamino)phenyl]ethenyl]-1-methyl-;Benz[cd]indolium,2-[2-[4-(dimethylamino)-2-ethoxyphenyl]ethenyl]-1-methyl-;and 3H-Indolium,2-[1-cyano-4,4-bis[4-(dimethylamino)phenyl]-1,3-butadienyl]-1,3,3-trimethyl-.58. A silicone composition according to claim 36, wherein saidcure-indicating dye is selected from the group consisting of4-[[4-(Dimethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Chloro-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;4-[[4-(Diethylamino)phenyl]imino]-1,4-dihydronapthalen-1-one;4-[[4-(Dimethylamino)phenyl]imino]-1,4-dihydronapthalen-1-one;4-[[2-methyl-4-(diethylamino)phenyl]imino]-1,4-dihydronapthalen-1-one;3-Methoxy-4-[[2-methyl-4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;2-Methyl-4-[[4-(4-morpholinyl)phenyl]imino]-2,5-cyclohexadien-1-one;2,5-Dichloro-4-[[4-(diethylamino)phenyl]imino]-2,5-cyclohexadien-1-one;3-[[4-(Diethylamino)-2-methylphenyl]imino]-6-oxo-N-phenyl-1,4-cyclohexadiene-1-carboxamide;5-[[4-(Diethylamino)-2-methylphenyl]imino]-8-(5H)-quinolinone;2,6-Dichloro-4-[[4-(acetamido)phenyl]imino]-2,5-cyclohexadien-1-one;4-(1-naphthylimino)-2,5-cyclohexadien-1-one;4-(2-naphthylimino)-2,5-cyclohexadien-1-one;2,5-Bis(phenylamino)-4(phenylimino)-2,5-cyclohexadien-1-one;4-[5,5-Bis[(trifluoromethyl)sulfonyl]-2,4-pentadienylidene]-1,4-dihydro-1-methylquinoline;6,6-Bis[4-(dimethylamino)phenyl]1,3,5-hexatriene-1,1-bis(sulfonylfluoride);4-[4,4-Bis[(trifluoromethyl)sulfonyl]-1,3-butadienyl]-N,N-dimethylbenzenamine;and4-[3-[4-(Dimethylamino)phenyl]-2-propenylidene]-2-phenyl-5(4H)-oxazolone.59. A silicone composition comprising:a curable silicone polymercontaining between 1 and 5,000 dimethyl siloxy bridging groups and atleast two vinyl groups; a crosslinker compound containing at least twoSiH groups and selected from the group consisting of organohydrosilanes,organohydrocyclopolysiloxanes, organohydropolysiloxanes, and branchedorganohydropolysiloxanes; a hydrosilation catalyst, wherein saidcatalyst comprises platinum and wherein said composition comprises aratio of platinum to functional groups between 1:2 and 1:1,000; and oneor more cure-indicating dyes that exhibit a color change within about 10minutes at 25° C. when 500 mg of said dye, about 500 ml ofdichloromethane, 100 ml of pentamethyldisiloxane, and 10 ml of ahydrosilation catalyst solution having between about 2 and 3 weightpercent platinum are mixed together, wherein said composition comprisesa ratio of SiH groups to functional groups between 1.3:1 and 4:1, andwherein said silicone composition exhibits a color change upon curing ofat least 10 ΔE* units.
 60. A method of monitoring the curing of acurable composition, comprising the steps of:mixing a compound havingtwo or more ethylenic functional groups; a crosslinker compoundcontaining at least 2 SiH groups; a hydrosilation catalyst; and acure-indicating dye that exhibits a color change, in a dye evaluationtest, within about 10 minutes at 25° C. when 500 mg of said dye, about500 ml of dichloromethane, 100 ml of pentamethyldisiloxane, and 10 ml ofa hydrosilation catalyst solution having between about 2 and 3 weightpercent platinum are mixed together; and observing said composition,wherein said composition has a first color before the cure reaction iseffected and a second color after the cure reaction has been effectedand wherein said first and second colors differ by at least 5 ΔE* units.61. A method of monitoring the curing of a curable composition accordingto claim 60, wherein the observation step is performed using the humaneye.
 62. A method of monitoring the curing of a curable compositionaccording to claim 60, wherein the second color of said curablecomposition is visually compared to a reference color standard andwherein the color difference between the reference color standard andthe second color of said curable composition is less than 3 ΔE* units.63. A method of monitoring the curing of a curable composition accordingto claim 60, wherein the first color of said curable composition isvisually compared to a reference color standard and wherein the colordifference between the reference color standard and the first color ofsaid curable composition is less than 3 ΔE* units.
 64. A method ofmonitoring the curing of a curable composition according to claim 62,wherein said reference color standard is selected from the groupconsisting of printed cards, printed labels, colored paper, coloredplastic parts, painted parts, colored ceramic parts, and colored curablecompositions.
 65. A method of monitoring the curing of a curablecomposition according to claim 60, wherein the observation step isperformed using a colorimeter, fluorimeter or spectrophotometer.
 66. Amethod of monitoring the curing of a curable composition according toclaim 65, wherein said curable composition is a coating composition andwherein said colorimeter, fluorimeter or spectrophotometer is utilizedon-line to monitor said color change.
 67. A method of monitoring thecuring of a curable composition according to claim 64, wherein saidfirst and second colors differ by at least 15 ΔE* units.
 68. A method ofmonitoring the curing of a curable composition according to claim 60,wherein said curable composition is an impression material.
 69. A methodof monitoring the curing of a curable composition according to claim 68,wherein the color of said impression material is visually compared to areference color standard selected from the group consisting of printedcards, printed labels, colored plastic parts, painted parts, coloredceramic parts, and colored curable compositions and wherein the colordifference between the reference color standard and the second color ofsaid impression material is less than 3 ΔE* units.